JP2015161824A - Toner for electrostatic charge image development - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner for electrostatic charge image development that has excellent reproducibility irrespective of a variation in a fixing temperature.SOLUTION: There is provided a toner for electrostatic charge image development that includes at least a binder resin including a styrene-acrylic resin and a styrene-acrylic modified polyester resin, a colorant represented by the following general formula (1), and a copper complex compound described later, where the content of the styrene-acrylic modified polyester resin is 10 to 40 mass% relative to the total mass of the binder resin.

Description

  The present invention relates to a toner for developing an electrostatic image.

  Color image formation by electrophotography was initially popular for office use, but due to its speed and ease of handling, it has recently become popular in the light printing field called on-demand printing (POD). It has become. This is due to the fact that the printing work required for the printing method is no longer necessary, and the image quality required for the printed image can be realized by the electrophotographic method due to the recent development of digital technology. It can be said. Due to the widespread use in the field of light printing, market demands are increasing to ensure a wider color reproduction area such as Japan Color certification for color reproducibility and to stabilize color reproduction even in continuous printing of multiple sheets. . As a color toner for forming such a color image, a yellow toner, a magenta toner, a cyan toner, or the like containing a binder resin (binder resin) made of a thermoplastic resin and a colorant of each color is used. ing.

  As means for realizing good color reproducibility, Patent Documents 1 and 2 disclose toners containing a colorant composed of a reaction compound produced by a reaction between a colorant precursor and a metal-containing compound. Patent Document 3 proposes a toner in which a colorant is contained in polyester particles coated with a vinyl resin.

JP 2009-282351 A JP 2010-2888 A JP 2009-169395 A

  However, the toners described in Patent Documents 1 to 3 have a problem that the color reproducibility is insufficient when the fixing temperature fluctuates such as continuous printing.

  Accordingly, an object of the present invention is to provide an electrostatic image developing toner that is excellent in color reproducibility even when the fixing temperature fluctuates.

  The inventors of the present invention have accumulated extensive research. As a result, surprisingly, the binder resin containing a styrene acrylic resin and a styrene acrylic modified polyester resin, a colorant, and a copper complex compound are included, and the content of the styrene acrylic modified polyester resin is the binder resin. The present inventors have found that the above problems can be solved by an electrostatic charge image developing toner characterized by being 10 to 40% by mass relative to the total mass of the present invention, and have completed the present invention.

  That is, the above object of the present invention is achieved by the following configuration.

  1. A binder resin including a styrene acrylic resin and a styrene acrylic modified polyester resin, a colorant represented by the following general formula (1), and a copper complex compound represented by the following general formula (2): The toner for developing an electrostatic charge image, wherein the content of the modified polyester resin is 10 to 40% by mass with respect to the total mass of the binder resin:

In the general formula (1),
Rx ₁ and Rx ₂ are each independently a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms,
Lx is a hydrogen atom or a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms,
Gx ₁ is a linear, branched, or cyclic alkyl group or unsubstituted C2-20 substituted,
Gx ₂ is a substituted or unsubstituted linear or branched alkyl group having 1 to 5 carbon atoms,
Gx ₃ is a hydrogen atom, a halogen atom, a group represented by Gx ₄ —CO—NH—, or a group represented by Gx ₅ —N (Gx ₆ ) —CO—, wherein Gx ₄ is a substituent. Gx ₅ and Gx ₆ are each independently a hydrogen atom or a substituent,
Qx ₁ , Qx ₂ , Qx ₃ , Qx ₄ , and Qx ₅ are each independently a hydrogen atom or a substituent,

In the general formula (2),
R ₁ is a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms,
R ₂ is a hydrogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfamoyl group, a sulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, a halogen atom, or a cyano group,
R ₃ is a substituted or unsubstituted aromatic hydrocarbon-containing group having 9 to 120 carbon atoms.

  2. 1. The styrene acrylic resin comprising at least two kinds of the styrene acrylic resins, at least one of which is a styrene acrylic resin having a content of structural units derived from methacrylic acid of 10 to 20% by mass. The toner for developing an electrostatic charge image according to 1.

  According to the present invention, it is possible to provide an electrostatic image developing toner that is excellent in color reproducibility even if the fixing temperature varies.

  The present invention includes at least a binder resin including a styrene acrylic resin and a styrene acrylic modified polyester resin, a colorant represented by the following general formula (1), and a copper complex compound represented by the following general formula (2). The toner for developing an electrostatic charge image is characterized in that the content of the styrene acrylic modified polyester resin is 10 to 40% by mass with respect to the total mass of the binder resin.

In the general formula (1),
Rx ₁ and Rx ₂ are each independently a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms,
Lx is a hydrogen atom or a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms,
Gx ₁ is a linear, branched, or cyclic alkyl group or unsubstituted C2-20 substituted,
Gx ₂ is a substituted or unsubstituted linear or branched alkyl group having 1 to 5 carbon atoms,
Gx ₃ is a hydrogen atom, a halogen atom, a group represented by Gx ₄ —CO—NH—, or a group represented by Gx ₅ —N (Gx ₆ ) —CO—, wherein Gx ₄ is a substituent. Gx ₅ and Gx ₆ are each independently a hydrogen atom or a substituent,
Qx ₁ , Qx ₂ , Qx ₃ , Qx ₄ , and Qx ₅ are each independently a hydrogen atom or a substituent.

In the general formula (2),
R ₁ is a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms,
R ₂ is a hydrogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfamoyl group, a sulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, a halogen atom, or a cyano group,
R ₃ is a substituted or unsubstituted aromatic hydrocarbon-containing group having 9 to 120 carbon atoms.

  The electrostatic image developing toner of the present invention having such a configuration (hereinafter also simply referred to as toner) is a toner having excellent color reproducibility even when the fixing temperature varies.

The detailed reason why the toner of the present invention is excellent in color reproducibility is unknown,
(I) By reducing the number of carbon atoms of the alkyl group represented by _{GX2 in} the general formula (1), the hydrophobicity of the colorant is lowered and the interaction with the binder resin is further increased. (II) The dispersion state of the colorant in the toner due to the ester groups in the binder resin and, if necessary, polar groups such as carboxyl groups contained in the binder resin. (III) Since the polyester resin has a sharp melt property, even if the fixing temperature fluctuates, a combination of mechanisms such as the state of the binder resin after fixing is combined and the above effect is achieved. It is considered to be obtained. In addition, the said mechanism is based on estimation and this invention is not limited to the said mechanism at all.

  Hereinafter, the configuration of the toner of the present invention will be described in detail.

[Binder resin]
The binder resin according to the present invention includes a styrene acrylic resin and a styrene acrylic modified polyester resin, and the content of the styrene acrylic modified polyester resin is 10 to 40% by mass with respect to the total mass of the binder resin.

<Styrene acrylic modified polyester resin>
In this section, the styrene acrylic modified polyester resin will be described. Here, the “styrene acrylic modified polyester resin” means that a molecular chain of a styrene acrylic copolymer molecular chain (hereinafter also referred to as a styrene acrylic copolymer segment) is molecularly bonded to a polyester molecular chain (hereinafter also referred to as a polyester segment). A resin composed of polyester molecules with a structure. That is, the styrene acrylic modified polyester resin is a resin having a copolymer structure in which a styrene acrylic copolymer segment is covalently bonded to a polyester segment.

  In the present invention, the total content of styrene acrylic copolymer segments in the styrene acrylic modified polyester resin (hereinafter also referred to as “styrene acrylic modification amount”) is preferably 5 to 30% by mass, and preferably 5 to 20%. More preferably, it is mass%.

  Specifically, the amount of styrene acrylic modification is the total mass of the resin material used to synthesize the styrene acrylic modified polyester resin, that is, the unmodified polyester resin that becomes the polyester segment and the fragrance that becomes the styrene acrylic polymer segment. Aromatic vinyl monomer and (meth) acrylic acid ester monomer with respect to the total mass of the aromatic vinyl monomer and (meth) acrylic acid ester monomer and the total amount of both reactive monomers for bonding them The ratio of the mass of

  When the amount of styrene acrylic modification is in the above range, the affinity between the styrene acrylic modified polyester resin and the styrene acrylic resin is improved, and the dispersion of the toner is improved.

  Further, in the toner of the present invention, an aliphatic unsaturated dicarboxylic acid is used as the polyvalent carboxylic acid for forming the polyester segment of the styrene acrylic modified polyester resin, and the structure derived from the aliphatic unsaturated dicarboxylic acid is used for the polyester segment. It is preferable that a unit is contained.

  The aliphatic unsaturated dicarboxylic acid refers to a chain dicarboxylic acid having a vinylene group in the molecule. Content ratio of structural unit derived from aliphatic unsaturated dicarboxylic acid in structural unit derived from polyvalent carboxylic acid constituting polyester segment of styrene-acrylic modified polyester resin (hereinafter referred to as “specific unsaturated dicarboxylic acid content ratio” Is also preferably 25 mol% or more and 75 mol% or less.

  When the specific unsaturated dicarboxylic acid content is in the above range, the affinity with the styrene acrylic resin is kept good, and uniform toner particles can be obtained. In addition, color reproducibility is high.

  The structural unit derived from the aliphatic unsaturated dicarboxylic acid is preferably a structural unit derived from a compound represented by the following general formula (A).

In the general formula (A), R ¹ and R ² are each independently a hydrogen atom, a methyl group or an ethyl group, and n is 1 or 2.

  The styrene acrylic modified polyester resin used in the present invention is not particularly limited as long as the molecular structure has two types of segments of a polyester segment and a styrene acrylic copolymer segment. Specifically, a block copolymer structure in which a styrene acrylic copolymer segment is bonded to the end of a polyester segment, or a graft copolymer structure in which a branched structure of a styrene acrylic copolymer segment is formed on a polyester segment. Is mentioned.

  The method for producing the styrene acrylic modified polyester resin used in the present invention is not particularly limited as long as it is a method capable of forming a polymer having a structure in which a polyester segment and a styrene acrylic copolymer segment are molecularly bonded. It is not something. Specific methods for producing the styrene acrylic modified polyester resin include, for example, the methods shown below.

[Method for producing styrene acrylic-modified polyester resin]
The method for producing the styrene acrylic modified polyester resin used in the present invention is not particularly limited as long as it is a method capable of forming a polymer having a structure in which a polyester segment and a styrene acrylic copolymer segment are molecularly bonded. It is not something. Specific methods for producing the styrene acrylic modified polyester resin include, for example, the following three methods.

  (A) A polyester segment is polymerized in advance, and both reactive monomers are reacted with the polyester segment, and an aromatic vinyl monomer and a (meth) acrylic acid ester for forming a styrene acrylic copolymer segment. A method of forming a styrene acrylic copolymer segment by reacting a monomer.

  (B) A styrene acrylic copolymer segment is polymerized in advance, the reactive monomer is reacted with the styrene acrylic copolymer segment, and a polyvalent carboxylic acid and a polyhydric alcohol for forming a polyester segment are further added. A method of forming a polyester segment by reacting.

  (C) A method in which a polyester segment and a styrene acrylic copolymer segment are respectively polymerized in advance, and both are reacted with each other to react them.

  In this specification, the both reactive monomers are a site capable of reacting with a carboxyl group (—COOH) and / or a hydroxy group (—OH) remaining in the polyester segment of the styrene acrylic-modified polyester resin, and a vinyl monomer. It is a monomer having a reactive site.

(A) A method for producing a styrene-acrylic modified polyester resin by forming a polyester segment in advance and performing a polymerization reaction to form a styrene-acrylic copolymer segment in the presence of the polyester segment. Carboxylic acid and polyhydric alcohol are subjected to a condensation reaction for polymerization to form a polyester segment. Next, in the presence of the polyester segment, a vinyl monomer such as an aromatic vinyl monomer or a (meth) acrylic acid ester monomer is polymerized to form a styrene acrylic copolymer segment. At this time, both reactive monomers are also used. That is, when this bi-reactive monomer reacts with a carboxyl group (—COOH) and / or a hydroxy group (—OH) in the polyester segment, the polyester segment has a structure in which the bi-reactive monomers are bonded. Then, in the presence of the polyester segment to which the both reactive monomers are bonded, an aromatic vinyl monomer and a (meth) acrylic acid ester monomer are added by radical polymerization or the like, thereby producing a styrene acrylic copolymer. A coalesced segment is formed. At this time, a styrene acrylic modified polyester resin having a structure in which the polyester segment and the styrene acrylic copolymer segment are molecularly bonded through a site capable of reacting with the vinyl monomer of the both reactive monomers bonded to the polyester segment. Can be formed.

  That is, the method of (A) is “to form a styrene acrylic copolymer molecular chain by polymerizing at least an aromatic vinyl monomer and a (meth) acrylic acid ester monomer in the presence of a polyester molecular chain. This corresponds to the “Yes” method. In the method (A), before the aromatic vinyl monomer and the (meth) acrylic acid ester monomer (vinyl monomer) are added to the reaction system, the both reactive monomers are added. There are a method of bonding with polyester and a method of carrying out the reaction by adding the both reactive monomers together with the vinyl monomer. The method (1) is preferably used when forming a styrene-acrylic modified polyester resin having a block copolymer structure in which a styrene-acrylic copolymer molecular chain is molecularly bonded to the end of a polyester molecular chain, as will be described later. Is the method.

(B) A method of polymerizing a styrene acrylic copolymer segment in advance and performing a polymerization reaction to form a polyester segment in the presence of the styrene acrylic copolymer segment to produce a styrene acrylic modified polyester resin. First, a vinyl monomer such as an aromatic vinyl monomer and a (meth) acrylic acid ester monomer is subjected to an addition reaction to form a styrene acrylic copolymer segment. Next, in the presence of the styrene acrylic copolymer segment, a polyvalent carboxylic acid and a polyhydric alcohol are polymerized to form a polyester segment. At this time, in addition to the polyvalent carboxylic acid and the polyhydric alcohol, an amphoteric monomer is also used. That is, by reacting the both reactive monomers with the styrene acrylic copolymer segment, the styrene acrylic copolymer segment has a structure in which the both reactive monomers are bonded. And a polyester segment is formed by carrying out the condensation reaction of polyhydric carboxylic acid and polyhydric alcohol in presence of the styrene acrylic copolymer segment which combined the said both reactive monomer. At this time, the styrene acrylic copolymer segment and the polyester segment were molecularly bonded via a site capable of reacting with the polyvalent carboxylic acid and / or polyhydric alcohol of the both reactive monomers bonded to the styrene acrylic copolymer segment. A styrene acrylic modified polyester resin having a structure can be formed.

(C) A method in which a polyester segment and a styrene acrylic copolymer segment are formed in advance, and these are combined to produce a styrene acrylic modified polyester resin. In this method, first, a polyvalent carboxylic acid and a polyhydric alcohol are used. A polyester segment is formed by a condensation reaction. In addition to the reaction system for forming the polyester segment, an aromatic vinyl monomer and a (meth) acrylic acid ester monomer are addition-polymerized to form a styrene acrylic copolymer segment. Next, a system in which the polyester segment and the styrene acrylic copolymer segment coexist is formed, and the both reactive monomers are added thereto. A styrene acrylic modified polyester resin having a structure in which the polyester segment and the styrene acrylic copolymer segment are molecularly bonded can be formed via the both reactive monomers.

  Among the forming methods (A) to (C) described above, the method (A) is easy to form and produce a styrene acrylic modified polyester resin having a structure in which a styrene acrylic copolymer molecular chain is bonded to the end of the polyester molecular chain. This is preferable because the process can be simplified. In the method (A), since the polyester segment is formed in advance and then the both reactive monomers are added and bonded to the polyester segment, the both reactive monomers have a very high probability of binding to the end of the polyester segment. Become. Therefore, a styrene acrylic modified polyester resin having a structure defined in the present invention can be reliably formed, which is preferable.

  In the forming methods (A) to (C), it is preferable to perform a heat treatment in order to uniformly mix a compound such as a polymerizable monomer used for forming the styrene acrylic modified polyester. Specifically, 80-125 degreeC is preferable, 90-120 degreeC is more preferable, and 95-115 degreeC is further more preferable. By heating under the above temperature range, compounds such as polyester molecular chain, aromatic vinyl monomer, (meth) acrylic acid ester monomer and the like are easily mixed, and in forming a styrene acrylic modified polyester resin. preferable.

  The polyester segment constituting the styrene acrylic modified polyester resin used in the present invention preferably has a glass transition temperature of 40 to 70 ° C, more preferably 50 to 65 ° C when it is a single polyester molecular chain. When the glass transition temperature is 40 ° C. or higher, it is possible to form a toner image in which the polyester segments are appropriately aggregated during fixing and the hot offset phenomenon does not occur. In addition, since the glass transition temperature is 70 ° C. or lower, a low-temperature fixing toner that melts a toner image at a lower temperature than before can be produced without inhibiting the melting of the styrene-acrylic copolymer resin during fixing. This is preferable.

  Further, the polyester segment constituting the styrene acrylic modified polyester resin preferably has a weight average molecular weight (Mw) of 1,500 to 60,000, and 3,000 to 40,000 when it is a single polyester molecular chain. Is more preferable. By setting the weight average molecular weight to 1,500 or more, an appropriate cohesive force can be imparted to the entire toner resin, and a toner image that hardly causes a hot offset phenomenon during fixing can be formed. Further, when the weight average molecular weight is 60,000 or less, sufficient melting can be achieved by heating in a short time, and a firm fixed image can be formed by cooling. Therefore, it is preferable in forming a toner image by low-temperature fixing. The weight average molecular weight of the polyester segment and the styrene acrylic copolymer segment can be measured by gel permeation chromatography (GPC).

  The styrene acrylic copolymer segment constituting the styrene acrylic modified polyester resin used in the present invention preferably has a glass transition temperature (Tg) of 35 to 80 ° C. when it is a single styrene acrylic copolymer molecular chain. The thing of 40-60 degreeC is more preferable. The glass transition temperature is calculated by the FOX equation shown below.

  In the FOX formula, Wx represents the mass fraction of monomer x, and Tgx represents the glass transition temperature of the homopolymer of monomer x. Here, the amphoteric monomer is not used when calculating the glass transition temperature.

  The styrene acrylic copolymer segment preferably has a weight average molecular weight (Mw) of 2,000 to 100,000.

  Specific examples of the both reactive monomers include a vinyl compound having a carboxyl group such as acrylic acid, methacrylic acid, fumaric acid and maleic acid, and a carboxylic acid anhydride such as maleic anhydride. The amount of the both reactive monomers used is preferably 0.1 to 5.0% by mass, and preferably 0.5 to 3.0, assuming that the total mass of the compounds used for forming the styrene acrylic modified polyester resin is 100% by mass. The mass% is more preferable. Here, the compound used for formation of a styrene acrylic modified polyester resin is a polyester segment, an aromatic vinyl monomer, a (meth) acrylic acid ester monomer, and a bireactive monomer.

  The amount of the aromatic vinyl monomer and (meth) acrylic acid ester monomer used in forming the styrene acrylic modified polyester resin used in the present invention is the compound used for forming the styrene acrylic modified polyester resin described above. When the total mass is 100 mass%, the total amount is preferably 5 to 30 mass%, more preferably 5 to 20 mass%. That is, it is a range that coincides with the above-mentioned styrene acrylic modification amount.

  When the total proportion of the aromatic vinyl monomer and the (meth) acrylic acid ester monomer is in the above range, the affinity between the styrene acrylic modified polyester resin and the styrene acrylic resin is appropriately controlled. When the ratio is too small, sufficient heat storage stability and chargeability cannot be obtained for the obtained toner. On the other hand, when the ratio is excessive, the resulting styrene acrylic modified polyester resin has a high softening point, so that the resulting toner cannot obtain sufficient low-temperature fixability as a whole.

  The polyester segment constituting the styrene acrylic modified polyester resin used in the present invention is formed by polycondensation reaction of a known polycarboxylic acid and a polyhydric alcohol in the presence of a catalyst. The polyester segment can be a derivative of the aforementioned polyvalent carboxylic acid or polyhydric alcohol used as a raw material. The polyvalent carboxylic acid derivative includes an alkyl ester, an acid anhydride, or an acid chloride of the polyvalent carboxylic acid. Etc. Polyhydric alcohol derivatives include polyhydric alcohol ester compounds and hydroxycarboxylic acids.

  Hereinafter, specific examples of polyvalent carboxylic acid and polyhydric alcohol that can be used for forming the polyester segment will be described. Examples of the polyvalent carboxylic acid include known divalent carboxylic acids and trivalent or higher carboxylic acids called aliphatic dicarboxylic acids and aromatic dicarboxylic acids. Specific examples of the divalent carboxylic acid include, for example, oxalic acid, succinic acid, maleic acid, mesaconic acid, adipic acid, β-methyladipic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid. Acid, dodecanedicarboxylic acid, fumaric acid, citraconic acid, diglycolic acid, cyclohexane-3,5-diene-1,2-dicarboxylic acid, malic acid, citric acid, malonic acid, pimelic acid, tartaric acid, phthalic acid, isophthalic acid Terephthalic acid, tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, hexahydroterephthalic acid, p-carboxyphenylacetic acid, p-phenylenediacetic acid, m-phenylenediglycolic acid, p-phenylenediglycolic acid, o-phenylenediglycol Glycolic acid, diphenylacetic acid, diphenyl-p, '- dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, anthracene dicarboxylic acid, and dodecenylsuccinic acid. Specific examples of the trivalent or higher carboxylic acid include trimellitic acid, pyromellitic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, pyrenetricarboxylic acid, and pyrenetetracarboxylic acid. These polyvalent carboxylic acids can be used singly or in combination of two or more.

  Specific examples of the polyhydric alcohol include known dihydric alcohols and trihydric or higher alcohols. Specific examples of the dihydric alcohol include, for example, ethylene glycol, propylene glycol, butanediol, diethylene glycol, hexanediol, cyclohexanediol, octanediol, decanediol, dodecanediol, ethylene oxide adduct of bisphenol A, and propylene oxide of bisphenol A. Examples include adducts. Specific examples of the trivalent or higher alcohol include glycerin, pentaerythritol, hexamethylol melamine, hexaethylol melamine, tetramethylol benzoguanamine, tetraethylol benzoguanamine, and the like. These polyhydric alcohols can be used alone or in combination of two or more.

  As a method for forming the polyester segment, a conventionally known method for forming a polyester segment by polycondensation reaction between a polycarboxylic acid and a polyhydric alcohol in the presence of a catalyst is employed. A known catalyst can also be used.

  In the styrene acrylic modified polyester resin, among the polyvalent carboxylic acids, it is preferable to use an aliphatic unsaturated dicarboxylic acid having a carbon-carbon unsaturated bond in the molecular structure. This aliphatic unsaturated dicarboxylic acid has an advantage that a structure in which a polyester segment and a styrene-acrylic copolymer segment are molecularly bonded can be formed without using the above-mentioned both reactive monomers. Therefore, it is preferable because it contributes to productivity improvement by reducing the types of compounds necessary for producing the styrene acrylic-modified polyester resin and simplifying the resin production process. Of course, even when the aliphatic unsaturated dicarboxylic acid is used, both reactive monomers may be used.

  The aliphatic unsaturated dicarboxylic acid is preferably fumaric acid, maleic acid or mesaconic acid.

  Moreover, it is preferable that the ratio of the aliphatic unsaturated dicarboxylic acid with respect to all the polyvalent carboxylic acids used for polyester segment formation is 20-75 mol%, and it is more preferable that it is 30-60 mol%.

  As a method for forming the polyester segment, a conventionally known method for forming a polyester segment by polycondensation reaction between a polycarboxylic acid and a polyhydric alcohol in the presence of a catalyst is employed. A known catalyst can also be used.

  The ratio of the polyhydric carboxylic acid to the polyhydric alcohol is preferably an equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] of the polyhydric alcohol to the carboxyl group [COOH] of the polyhydric carboxylic acid. 0.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2.

  The polyester segment may have a partially branched structure or a crosslinked structure by appropriately selecting the valence of the polyvalent carboxylic acid and / or polyhydric alcohol used.

Next, the compound which forms a styrene acrylic copolymer segment is demonstrated. The polyester segment constituting the styrene acrylic modified polyester resin (A) used in the present invention is formed by addition polymerization of at least an aromatic vinyl monomer and a (meth) acrylic acid ester monomer. is there. The aromatic vinyl monomer here includes, in addition to styrene represented by the structural formula of CH ₂ ═CH—C ₆ H ₅ , those having a structure having a known side chain or functional group in the styrene structure. It is a waste. In addition, the (meth) acrylic acid ester monomer referred to here is an acrylic acid ester derivative or methacrylic acid in addition to the acrylic acid ester compound or methacrylic acid ester compound represented by CH ₂ = CHCOOR (R is an alkyl group). It includes an ester compound having a known side chain or functional group in the structure of an ester derivative or the like.

  Specific examples of the aromatic vinyl monomer and (meth) acrylic acid ester monomer capable of forming a styrene acrylic copolymer segment are shown below, but the styrene acrylic copolymer segment used in the present invention is not limited. What can be used for formation is not limited to the following.

  Specific examples of the aromatic vinyl monomer include, for example, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4- Dimethyl styrene, 3,4-dichlorostyrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl Examples include styrene. These aromatic vinyl monomers can be used alone or in combination of two or more.

  Specific examples of the (meth) acrylic acid ester monomer include, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, and n-octyl acrylate. Acrylate monomers such as 2-ethylhexyl acrylate, stearyl acrylate, lauryl acrylate, phenyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, lauryl methacrylate DOO, phenyl methacrylate, diethylaminoethyl methacrylate, methacrylic acid ester monomers such as dimethylaminoethyl methacrylate.

  These acrylic acid ester monomers or methacrylic acid ester monomers can be used alone or in combination of two or more. That is, forming a copolymer using an aromatic vinyl monomer and two or more kinds of acrylate monomers, and combining an aromatic vinyl monomer and two or more kinds of methacrylic ester monomers. Can be used to form a copolymer, or an aromatic vinyl monomer and an acrylic acid ester monomer and a methacrylic acid ester monomer can be used in combination to form a copolymer. .

  The method for forming the styrene-acrylic copolymer segment is not particularly limited, and examples thereof include a method of polymerizing monomers using various known polymerization initiators. The timing of addition of the polymerization initiator is not particularly limited, but the aromatic vinyl monomer and (meth) acryl for forming the polymerization of the styrene-acrylic copolymer segment are easy in that radical polymerization is easily controlled. It is preferable to add the acid ester monomer after mixing.

  Specific examples of the polymerization initiator include, for example, hydrogen peroxide, acetyl peroxide, cumyl peroxide, di-t-butyl peroxide, propionyl peroxide, benzoyl peroxide, chlorobenzoyl peroxide, dichlorobenzoyl peroxide, Bromomethylbenzoyl oxide, lauroyl peroxide, ammonium persulfate, sodium persulfate, potassium persulfate, diisopropyl peroxycarbonate, tetralin hydroperoxide, 1-phenyl-2-methylpropyl-1-hydroperoxide, t-butyl pertriphenylacetate Hydroperoxide, t-butyl formate, per-acetate-t-butyl, perbenzoate-t-butyl, perphenylacetate-t-butyl, permethoxyacetate-t-butyl, per-N- (3-toluyl) palmitin Peroxides such as acid-t-butyl; 2,2′-azobis (2- Minodipropane) hydrochloride, 2,2′-azobis- (2-aminodipropane) nitrate, 1,1′-azobis (sodium 1-methylbutyronitrile-3-sulfonate), 4,4′-azobis-4 -Azo compounds such as cyanovaleric acid and poly (tetraethylene glycol-2,2'-azobisisobutyrate).

  Moreover, when forming resin particles by an emulsion polymerization method, a water-soluble radical polymerization initiator can be used. Examples of the water-soluble polymerization initiator include persulfates such as potassium persulfate and ammonium persulfate, azobisaminodipropane acetate, azobiscyanovaleric acid and its salts, hydrogen peroxide, and the like.

  In the polymerization of the styrene acrylic copolymer segment, a generally used chain transfer agent can be used for the purpose of adjusting the molecular weight of the styrene acrylic copolymer segment. The chain transfer agent is not particularly limited, and examples thereof include alkyl mercaptans such as n-octyl mercaptan, mercapto fatty acid esters, and the like.

  The chain transfer agent is preferably mixed together in the mixing step of the aromatic vinyl monomer and the (meth) acrylate monomer for forming the polymerization of the styrene acrylic copolymer segment.

  The amount of chain transfer agent added varies depending on the molecular weight and molecular weight distribution of the desired styrene acrylic polymer segment. Specifically, aromatic vinyl monomers and (meth) acrylic acid ester monomers, and both reactive monomers are used. It is preferable to add in the range of 0.1-5 mass% with respect to the total amount.

  In the production of the styrene acrylic modified polyester resin, it is practically preferable that the volatile organic substance from the emulsion such as the amount of residual monomer after polymerization is suppressed to 1,000 ppm or less, more preferably 500 ppm or less, and still more preferably. 200 ppm or less.

  As the aromatic vinyl monomer and (meth) acrylic acid ester monomer for forming the styrene acrylic copolymer segment, styrene or its derivatives are often used from the viewpoint of obtaining excellent chargeability and image quality characteristics. It is preferable. Specifically, the amount of styrene or its derivative used in all monomers (aromatic vinyl monomer and (meth) acrylic acid ester monomer) used to form the styrene acrylic polymer segment. It is preferable that it is 50 mass% or more.

  In the present invention, the content of the styrene acrylic modified polyester resin is 10 to 40% by mass with respect to the total mass of the binder resin. When the content is less than 10% by mass, the effect of improving color reproducibility when the fixing temperature varies cannot be obtained. On the other hand, when the content exceeds 40% by mass, the particle size distribution of the toner spreads. As a result, the toner charge amount distribution becomes wide, and image defects such as fogging due to toner scattering occur. The content is preferably 15 to 35% by mass, more preferably 20 to 30% by mass.

  The styrene acrylic modified polyester resin according to the present invention may be used alone or in combination of two or more.

<Styrene acrylic resin>
The styrene acrylic resin referred to in the present invention is formed by polymerization using at least an aromatic vinyl monomer and a (meth) acrylic acid ester monomer. Here, the aromatic vinyl monomer includes not only styrene represented by the structural formula of CH ₂ ═CH—C ₆ H ₅ but also a structure having a known side chain or functional group in the styrene structure. It is.

The (meth) acrylic acid ester monomer has a functional group having an ester bond in the side chain. _{Specifically,} CH 2 = CHCOOR (R is an alkyl group) other acrylic acid ester monomer represented _by, methacrylic acid ester represented by _{CH 2 = C (CH 3)} COOR (R is an alkyl group) Vinyl-based ester compounds such as monomers are included.

  Specific examples of the aromatic vinyl monomer and (meth) acrylic acid ester monomer capable of forming a styrene acrylic resin are shown below, but are not limited to those shown below.

  Examples of the aromatic vinyl monomer include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, Examples thereof include p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, and the like.

  The (meth) acrylic acid ester monomer is typically the following acrylic acid ester monomer and methacrylic acid ester monomer. Examples of the acrylic acid ester monomer include methyl acrylate, Examples include ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, lauryl acrylate, and phenyl acrylate phenyl. Examples of the methacrylic acid ester monomer include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate. Lauryl methacrylate, phenyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl methacrylate and the like.

  These aromatic vinyl monomers, acrylic acid ester monomers, or methacrylic acid ester monomers can be used alone or in combination of two or more.

  In addition to the copolymer formed only with the above-mentioned aromatic vinyl monomer and (meth) acrylic acid ester monomer, the styrene acrylic resin includes these aromatic vinyl monomer and (meth) acrylic. In addition to acid ester monomers, some are formed by using general vinyl monomers in combination. Although the vinyl monomer which can be used together when forming the styrene acrylic resin said by this invention below is illustrated, the vinyl monomer which can be used together is not limited to what is shown below.

(1) Olefins Ethylene, propylene, isobutylene, etc. (2) Vinyl esters Vinyl propionate, vinyl acetate, vinyl benzoate, etc. (3) Vinyl ethers Vinyl methyl ether, vinyl ethyl ether, etc. (4) Vinyl ketones Vinyl methyl ketone, Vinyl ethyl ketone, vinyl hexyl ketone, etc. (5) N-vinyl compounds N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidone, etc. (6) Others Vinyl compounds such as butadiene, vinyl naphthalene, vinyl pyridine, acrylonitrile, Acrylic acid or methacrylic acid derivatives such as methacrylonitrile, acrylamide and methacrylamide, vinyl acetate, maleic anhydride and the like.

  Moreover, it is also possible to produce a resin having a crosslinked structure by using the following polyfunctional vinyl monomer. Specific examples of the polyfunctional vinyl monomer include, for example, divinylbenzene, ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, neopentyl. Examples thereof include dimethacrylates and trimethacrylates of tertiary alcohols such as glycol dimethacrylate, neopentyl glycol diacrylate, hexylene glycol dimethacrylate, hexylene glycol diacrylate, pentaerythritol, and trimethylolpropane.

  0.001-5 mass% is preferable with respect to binder resin, and, as for the usage-amount of a polyfunctional vinyl monomer, 0.003-2 mass% is more preferable. By using the polyfunctional vinyl monomer, a gel component insoluble in tetrahydrofuran is generated. The gel component is preferably 40% by mass or less, more preferably 20% by mass or less of the entire binder resin. is there.

  Furthermore, it is also possible to use a vinyl monomer having an ionic dissociation group in the side chain as shown below. Specific examples of the ionic dissociation group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Specific examples of these vinyl monomers having an ionic dissociation group are shown below.

  Specific examples of the vinyl monomer having a carboxyl group include acrylic acid, methacrylic acid, maleic acid, itaconic acid, cinnamic acid, fumaric acid, maleic acid monoalkyl ester, itaconic acid monoalkyl ester, and the like. .

  Specific examples of the vinyl monomer having a sulfonic acid group include styrene sulfonic acid, allyl sulfosuccinic acid, 2-acrylamido-2-methylpropane sulfonic acid, and the like. Furthermore, specific examples of the vinyl monomer having a phosphate group include acid phosphooxyethyl methacrylate and 3-chloro-2-acid phosphooxypropyl methacrylate.

  The formation method in particular of a styrene acrylic resin is not restrict | limited, The method of superposing | polymerizing a monomer using a well-known polymerization initiator is mentioned. Specific examples of the polymerization initiator are the same as those described in the above section <Styrene Acrylic Modified Polyester Resin>, and thus the description thereof is omitted here.

  When forming the styrene acrylic resin used in the present invention, the content of the aromatic vinyl monomer and the (meth) acrylic acid ester monomer is not particularly limited, and the softening point temperature of the binder resin or It is possible to adjust appropriately from the viewpoint of adjusting the glass transition temperature. Specifically, the content of the aromatic vinyl monomer is preferably 40 to 95% by mass and more preferably 50 to 80% by mass with respect to the whole monomer. Moreover, 5-60 mass% is preferable with respect to the whole monomer, and, as for content of a (meth) acrylic acid ester monomer, 10-50 mass% is more preferable.

  The molecular weight of the styrene acrylic resin is preferably 2,000 to 1,000,000 in terms of weight average molecular weight (Mw). Further, the number average molecular weight (Mn) is preferably 1,000 to 100,000. Moreover, 1.5-100 are preferable and, as for molecular weight distribution (Mw / Mn), 1.8-70 are more preferable. By setting the weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the styrene acrylic resin within the above ranges, an offset is applied in the fixing step when printing is performed using the prepared toner. This is effective in preventing the occurrence of phenomena. The glass transition point temperature of the styrene acrylic resin formed by radical polymerization is preferably 30 to 70 ° C, and the softening point temperature is preferably 80 to 170 ° C. When the glass transition point temperature and the softening point temperature are in the above ranges, good fixability can be obtained. The molecular weight of the styrene acrylic resin can be measured by a gel permeation chromatograph (GPC) method.

  The styrene acrylic resins according to the present invention may be used alone or in combination of two or more. When using 2 or more types, it is preferable that at least 1 type is the styrene acrylic resin whose content of the structural unit derived from methacrylic acid is 10-20 mass%. Such a styrene acrylic resin has a carboxyl group, and it is considered that this carboxyl group further stabilizes the dispersion state of the colorant and further improves the effect of the present invention.

  As for content of the styrene acrylic resin whose content of the structural unit derived from methacrylic acid is 10-20 mass%, it is more preferable that it is 5-15 mass% with respect to the total mass of binder resin.

<Other binder resins>
The binder resin of the present invention may contain other resins in addition to the above styrene acrylic modified polyester resin and styrene acrylic resin. Examples of other resins include homopolymers of styrene or styrene derivatives such as polystyrene, poly p-chlorostyrene, and polyvinyl toluene; styrene-p-chlorostyrene copolymers, styrene-propylene copolymers, styrene- Vinyl toluene copolymer, styrene-vinyl naphthalene copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-butadiene-acrylonitrile copolymer Styrene copolymers such as polymers, styrene-acrylonitrile-indene copolymers, styrene-maleic acid copolymers, styrene-maleic acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyacetic acid Nyl, polyethylene, polypropylene, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorine And paraffin wax. These other resins can be used alone or in combination of two or more.

  The binder resin described above may have a single layer structure or a core-shell structure. The core-shell structure has a resin region (shell) having a relatively high glass transition temperature on the surface of resin particles (core particles) having a relatively low glass transition temperature containing a colorant or wax. The core-shell structure is not limited to a structure in which the shell completely covers the core, and includes, for example, a structure in which the shell does not completely cover the core particles and the core particles are exposed in some places.

  The cross-sectional structure of the core-shell structure can be confirmed using known means such as a transmission electron microscope (TEM) or a scanning probe microscope (SPM).

  The combination of the resins constituting the core-shell structure is not particularly limited, but it is preferable to use a styrene acrylic copolymer for the core portion and a styrene acrylic modified polyester resin for the shell portion.

[Colorant]
The colorant according to the present invention is a compound represented by the following general formula (1).

In the general formula (1), Rx ₁ and Rx ₂ are each independently substituted or are or unsubstituted straight, branched, or cyclic alkyl group. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, iso-amyl group, tert-pentyl group Group, neopentyl group, n-hexyl group, 3-methylpentan-2-yl group, 3-methylpentan-3-yl group, 4-methylpentyl group, 4-methylpentan-2-yl group, 1,3 -Dimethylbutyl group, 3,3-dimethylbutyl group, 3,3-dimethylbutan-2-yl group, n-heptyl group, 1-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5- Methylhexyl group, 1-ethylpentyl group, 1- (n-propyl) butyl group, 1,1-dimethylpentyl group, 1,4-dimethylpentyl group, 1,1-diethylpropyl group, 1 3,3-trimethylbutyl group, 1-ethyl-2,2-dimethylpropyl group, n-octyl group, 2-ethylhexyl group, 2-methylhexane-2-yl group, 2,4-dimethylpentan-3-yl Group, 1,1-dimethylpentan-1-yl group, 2,2-dimethylhexane-3-yl group, 2,3-dimethylhexane-2-yl group, 2,5-dimethylhexane-2-yl group, 2,5-dimethylhexane-3-yl group, 3,4-dimethylhexane-3-yl group, 3,5-dimethylhexane-3-yl group, 1-methylheptyl group, 2-methylheptyl group, 5- Methylheptyl group, 2-methylheptan-2-yl group, 3-methylheptan-3-yl group, 4-methylheptan-3-yl group, 4-methylheptan-4-yl group, 1-ethylhexyl group, 2 -D Ruhexyl group, 1-propylpentyl group, 2-propylpentyl group, 1,1-dimethylhexyl group, 1,4-dimethylhexyl group, 1,5-dimethylhexyl group, 1-ethyl-1-methylpentyl group, 1 -Ethyl-4-methylpentyl group, 1,1,4-trimethylpentyl group, 2,4,4-trimethylpentyl group, 1-isopropyl-1,2-dimethylpropyl group, 1,1,3,3-tetra Methylbutyl group, n-nonyl group, 1-methyloctyl group, 6-methyloctyl group, 1-ethylheptyl group, 1- (n-butyl) pentyl group, 4-methyl-1- (n-propyl) pentyl group 1,5,5-trimethylhexyl group, 1,1,5-trimethylhexyl group, 2-methyloctane-3-yl group, n-decyl group, 1-methylnonyl group, 1-ethyloxy Octyl group, 1- (n-butyl) hexyl group, 1,1-dimethyloctyl group, 3,7-dimethyloctyl group, n-undecyl group, 1-methyldecyl group, 1-ethylnonyl group, n-dodecyl group, 1 -Methylundecyl group, n-tridecyl group, n-tetradecyl group, 1-methyltridecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n- Eicosyl group, n-henicosyl group, n-docosyl group, n-tricosyl group, n-tetracosyl group, n-pentacosyl group, n-hexacosyl group, n-heptacosyl group, n-octacosyl group, n-nonacosyl group, or n -Triacontyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, 4-tert-butyl-silane Rohekishiru group, and the like.

  One or more hydrogen atoms of the alkyl group may be substituted with a substituent. Examples of the substituent include alkenyl groups (for example, vinyl group, allyl group, etc.), alkynyl groups (for example, ethynyl group, propargyl group, etc.), aromatic hydrocarbon groups (for example, phenyl group, naphthyl group, etc.), Aromatic heterocyclic group (for example, furyl group, thienyl group, pyridyl group, pyridazyl group, pyrimidyl group, pyrazyl group, triazyl group, imidazolyl group, pyrazolyl group, thiazolyl group, benzoimidazolyl group, benzoxazolyl group, quinazolyl group, Phthalazyl group, etc.), heterocyclic group (eg, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyloxy group) Group, dodecyloxy group, etc.), cycloalkoxy group (for example, cycl Pentyloxy group, cyclohexyloxy group, etc.), aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), alkylthio group (eg, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group) Etc.), a cycloalkylthio group (eg, cyclopentylthio group, cyclohexylthio group, etc.), an arylthio group (eg, phenylthio group, naphthylthio group, etc.), an alkoxycarbonyl group (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxy) Carbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), phosphoryl group (example) Dimethoxyphosphonyl, diphenylphosphoryl), sulfamoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylamino) Sulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), acyl group (for example, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2 -Ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group (For example, acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide group (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethyl group) Carbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (For example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, A hexylaminocarbonyl group, an octylaminocarbonyl group, a 2-ethylhexylaminocarbonyl group, a dodecylaminocarbonyl group, a phenylaminocarbonyl group, a naphthylaminocarbonyl group, a 2-pyridylaminocarbonyl group, etc.), a ureido group (for example, a methylureido group, Ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthylureido group, 2-pyridylaminoureido group, etc.), sulfinyl group (for example, methylsulfinyl group, ethylsulfinyl group, butyl) Sulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pi Dilsulfinyl group etc.), alkylsulfonyl group (eg methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group etc.), arylsulfonyl group (phenylsulfonyl group, naphthylsulfonyl) Group, 2-pyridylsulfonyl group, etc.), amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino group, dibutylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group) , Naphthylamino group, 2-pyridylamino group, etc.), azo group (eg, phenylazo group), alkylsulfonyloxy group (eg, methanesulfonyloxy group), cyano group, nitro group, halogen atom (eg, fluorine atom) Child, a chlorine atom, a bromine atom, etc.), a hydroxy group, etc., and these may further have a substituent. Among these substituents, an aromatic hydrocarbon group, an alkoxy group, a cycloalkoxy group, a halogen atom, or a hydroxy group is preferable.

Rx ₁ and Rx ₂ are each independently preferably an unsubstituted alkyl group or an alkyl group substituted with an alkoxy group, and more preferably an unsubstituted alkyl group.

The total number of carbon atoms contained in the alkyl group used in Rx ₁ and carbon atoms contained in the alkyl group used in Rx ₂ is preferably 8 or more, more preferably 12 or more, and 16 More preferably, it is the above.

In the general formula (1), Lx is a hydrogen atom or a substituted or unsubstituted linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms. Specific examples of the alkyl group are the same as the alkyl groups used in the above Rx ₁ and Rx ₂ , and thus detailed description thereof is omitted here. Further, specific examples of the substituent are the same as the substituents that can be used in the above Rx ₁ and Rx ₂ , and thus detailed description thereof is omitted here. Preferably it is a C1-C5 alkyl group, More preferably, it is a methyl group or an ethyl group.

In the above general formula (1), Gx ₁ is a substituted or unsubstituted C2-C20 linear, branched, or cyclic alkyl group. Specific examples of the alkyl group are the same as the alkyl groups used in Rx ₁ and Rx ₂ except for the methyl group, and thus detailed description thereof is omitted here. Further, specific examples of the substituent are the same as the substituents that can be used in the above Rx ₁ and Rx ₂ , and thus detailed description thereof is omitted here. Preferred is a branched alkyl group, more preferred is a tertiary alkyl group, and even more preferred is a t-butyl group.

In the above general formula (1), Gx ₂ is a substituted or unsubstituted linear or branched alkyl group having 1 to 5 carbon atoms. By employing the small alkyl group with a carbon number as gx _2, hydrophobicity of the colorant is reduced, the interaction with the binder resin becomes stronger. As a result, the dispersion state of the colorant becomes more stable, and the toner has excellent color reproducibility even when the fixing temperature fluctuates.

Specific examples of the alkyl group used in Gx ₂ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, and n-pentyl. Group, iso-amyl group, tert-pentyl group, or neopentyl group. Specific examples of the substituent are the same as the substituents that can be used for the above Rx ₁ and Rx ₂ , and thus detailed description thereof is omitted here. From the viewpoint of obtaining the effect of the present invention more effectively, a methyl group or an ethyl group is preferred.

In the general formula (1), Gx ₃ is a hydrogen atom, a halogen atom, a group represented by Gx ₄ —CO—NH—, or a group represented by Gx ₅ —N (Gx ₆ ) —CO—. In this case, Gx ₄ is a substituent, and Gx ₅ and Gx ₆ are each independently a hydrogen atom or a substituent.

Specific examples of the substituent used in Gx ₄ , Gx _5, and Gx ₆ include linear, branched, or cyclic having 1 to 20 carbon atoms in addition to the substituent that can be used in Rx ₁ and Rx _2. Of the alkyl group.

Qx ₁ , Qx ₂ , Qx ₃ , Qx ₄ , and Qx ₅ are each independently a hydrogen atom or a substituent. Specific examples of the substituent used in Qx ₁ , Qx ₂ , Qx ₃ , Qx ₄ , and Qx ₅ include linear groups having 1 to 20 carbon atoms in addition to the substituents that can be used in Rx ₁ and Rx _2. , Branched or cyclic alkyl groups. Qx ₁ , Qx ₂ , Qx ₃ , Qx ₄ , and Qx ₅ are each independently preferably a hydrogen atom, an alkyl group, a halogen atom, an alkoxy group, or an aryl group, and all of them are hydrogen atoms. More preferred.

  Hereinafter, although the more specific example of the coloring agent represented by the said General formula (1) is shown, this invention is not limited to these.

  Examples of the colorant represented by the general formula (1) according to the present invention include, for example, JP-A-63-226653, JP-A-10-193807, JP-A-11-78258, and JP-A-6-250357. No. 2-155893, No. 1-110565, No. 2-668, No. 2-28264, No. 2-53865, No. 2-53866, British Patent No. 1,252,418 Specification, JP-A-64-63194, JP-A-2-208094, JP-A-3-205189, JP-A-2-265991, JP-A-2-310087, JP-A-2-53866, Kaihei 4-91987, JP 63-205288, JP 3-226750, British Patent 1,183,515, JP 4-190348 JP-A-63-113077, JP-A-3-275767, JP-A-4-13774, JP-A-4-89287, JP-A-7-175187, JP-A-10-60296, JP-A-11-. It can be synthesized with reference to conventionally known methods described in JP-A-78258, JP-A-2004-13834, JP-A-2006-350300 and the like.

  These colorants may be used alone or in combination of two or more. The content of the colorant is preferably 0.5 to 10% by mass and more preferably 1 to 7% by mass with respect to the whole toner.

[Copper complex compound]
The copper complex compound according to the present invention is a compound represented by the following general formula (2). The copper complex compound can improve the light resistance and dispersion stability of the colorant.

  The compound represented by the general formula (2) can also be represented by using the limiting structural formulas of the following general formula (2a) and the following general formula (2b). In the present invention, the compound represented by the general formula (2), the compound represented by the following general formula (2a), and the compound represented by the following general formula (2b) are essentially the same, and are distinguished from each other. Not. The distinction between a covalent bond (indicated by −) and a coordination bond (indicated by...) Is also a formal one and does not represent an absolute distinction.

In the general formulas (2a) and (2b), R ₁ , R ₂ , and R ₃ are groups having the same meaning as in the general formula (2).

The copper complex compound in the present invention is preferably obtained by synthesizing a compound represented by the following general formula (2-1) and then reacting with a divalent copper compound. The method for synthesizing this copper complex compound can be synthesized according to the method described in “Chelate Chemistry (5) Complex Chemistry Experimental Method [I] (Edited by Nanedo)”. Examples of the divalent copper compound used include copper (II) chloride, copper (II) acetate, and copper perchlorate. Further, the copper complex compound used in the present invention may have a neutral ligand according to the central metal, representative ligands include H 2 _O or NH _3.

In the general formula (2-1), R ₁ , R ₂ , and R ₃ are groups having the same meaning as in the general formula (2).

In General Formula (2), General Formula (2a), General Formula (2b), and General Formula (2-1), R ₁ is a substituted or unsubstituted straight chain having 1 to 20 carbon atoms, A branched or cyclic alkyl group. Specific examples of the alkyl group are the same as the alkyl groups that can be used for Rx ₁ and Rx ₂ in the general formula (1) in the section of the colorant, and thus detailed description thereof is omitted here.

  One or more hydrogen atoms of the alkyl group may be substituted with a substituent. Examples of the substituent include alkenyl groups (eg, vinyl group, allyl group, etc.), alkynyl groups (eg, ethynyl group, propargyl group, etc.), aryl groups (eg, phenyl group, naphthyl group, etc.), heteroaryl groups (For example, furyl group, thienyl group, pyridyl group, pyridazyl group, pyrimidyl group, pyrazyl group, triazyl group, imidazolyl group, pyrazolyl group, thiazolyl group, benzoimidazolyl group, benzoxazolyl group, quinazolyl group, phthalazyl group, etc.) Heterocyclic group (for example, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxy group (for example, methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group) , Cyclopentyloxy group, cyclohexyloxy Group), aryloxy group (for example, phenoxy group, naphthyloxy group, etc.), alkylthio group (for example, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, cyclopentylthio group, cyclohexyl) Thio group etc.), arylthio group (eg phenylthio group, naphthylthio group etc.), alkoxycarbonyl group (eg methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group etc.) Aryloxycarbonyl group (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfamoyl group (eg, aminosulfonyl group, methylaminosulfonyl group, dimethylaminos) Phonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), acyl group (for example, Acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group (For example, acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, Phenylcarbonyloxy group, etc.), amide groups (eg, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octyl) Carbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, Cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylamino Carbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthyl group) Ureido group, 2-pyridylaminoureido group, etc.), sulfinyl group (for example, methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group, etc.), alkylsulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group) Group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group (phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (for example, amino group, ethylamino group, dimethylamino group, Butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, etc., cyano group, nitro group, halogen atom (for example, chlorine atom, bromine atom, fluorine) Atoms, iodine atoms, etc.), and these groups may be further substituted with the same groups.

R ₁ is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a linear alkyl group having 1 to 4 carbon atoms, still more preferably a methyl group or an ethyl group, and particularly preferably methyl. It is a group.

R ₂ is a hydrogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfamoyl group, a sulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, a halogen atom, or a cyano group. More specifically, an alkoxycarbonyl group such as a methyloxycarbonyl group, an ethyloxycarbonyl group, a butyloxycarbonyl group, an octyloxycarbonyl group or a dodecyloxycarbonyl group; an aryloxycarbonyl such as a phenyloxycarbonyl group or a naphthyloxycarbonyl group Group: aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group Sulfamoyl groups such as 2-pyridylaminosulfonyl group; methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclohexyl Rusulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group and other sulfinyl groups; methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2- Alkylsulfonyl groups such as ethylhexylsulfonyl group and dodecylsulfonyl group; arylsulfonyl groups such as phenylsulfonyl group, naphthylsulfonyl group and 2-pyridylsulfonyl group; acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group Octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl Boniru acyl groups such as a halogen atom (e.g., chlorine atom, bromine atom, a fluorine atom, an iodine atom), a cyano group.

R ₂ is preferably an alkoxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group or a cyano group, more preferably an alkoxycarbonyl group, an acyl group or a cyano group, still more preferably a cyano group.

R ₃ is a substituted or unsubstituted aromatic hydrocarbon-containing group having 9 to 120 carbon atoms.

Here, the aromatic hydrocarbon structure-containing group having 9 to 120 carbon atoms means that the total number of carbon atoms in R ₃ is 9 to 120, and an aromatic hydrocarbon structure at an arbitrary position in R ₃ Refers to a group containing Examples of the aromatic hydrocarbon structure include an aryl group (for example, a phenyl group, a naphthyl group, etc.). For example, when the aromatic hydrocarbon structure is a phenyl group, an arbitrary substituent having 3 or more carbon atoms is further included. Together with this, R ₃ is formed. In this case, it may have 3 or more substituents having 1 carbon atom, and may have 1 or more substituents each having 1 carbon atom and 2 substituents having 2 carbon atoms. The total number of carbon atoms in R ₃ is preferably 9 to 40, more preferably 12 to 40, and still more preferably 14 to 30.

R ₃ is preferably a group represented by the following general formula (3).

In the general formula (3), L represents a linear or branched alkylene group having 1 to 15 carbon atoms, —SO ₂ O—, —OSO ₂ —, —SO ₂ —, —CO—, —O. _{-, - S -, - SO} 2 NH -, - NHSO 2 -, - CONH -, - NHCO -, - COO-, and divalent alone or in combination with it based on the linking group selected from -OOC- the stands, * in, bound to the oxygen atom adjacent to R ₃ in the general formula (2).

  Specific examples of the linear or branched alkylene group having 1 to 15 carbon atoms include, for example, a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a propylene group, an ethylethylene group, a pentamethylene group, and a hexamethylene group. Group, 2,2,4-trimethylhexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, tridecamethylene group, tetradecamethylene group, pentadecamethylene group Etc.

L may have a substituent, and examples of the substituent include the same groups as the substituent used in R ₁ of the general formula (2).

The divalent linking group represented by L is preferably an alkylene group or a group containing an alkylene group. The group containing an alkylene group only needs to contain an alkylene group at an arbitrary position in the divalent linking group represented by L. Specifically, the alkylene group, —SO ₂ O—, —OSO _{2 -, - SO 2 -, -} CO -, - O -, - S -, - SO 2 NH -, - NHSO 2 -, - CONH -, - NHCO -, - COO-, and it is selected from -OOC- A group formed by combining one or more divalent linking groups.

R ₄ represents an aryl group (for example, a phenyl group, a naphthyl group, etc.).

  Specific examples of the divalent linking group represented by L are shown below, but the present invention is not limited thereto.

L is bonded to an oxygen atom adjacent to R ₃ in the general formula (2) or R ₄ in *.

R ₃ and R ₄ may have a substituent, and examples of the substituent include the same groups as the substituent used in R ₁ of the general formula (2).

Preferable substituents for substituting L, R ₃ and R ₄ include alkyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkoxycarbonyl group, aryloxycarbonyl group, sulfamoyl group, acyl group, acyloxy group, Amide group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, amino group, cyano group, nitro group, halogen atom, more preferably alkyl group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group , Sulfamoyl group, acyl group, acyloxy group, amide group and carbamoyl group, more preferably alkyl group, alkoxy group, aryloxy group, alkoxycarbonyl group, acyloxy group and amide group.

R ₄ is preferably a phenyl group, more preferably a phenyl group having a substituent, and further preferably a phenyl group having an alkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an acyloxy group, or an amide group. Particularly preferred is a phenyl group having an alkyl group or an alkoxy group.

R ₃ or the general formula (3) is more preferably a group represented by the following general formula (3-1).

In the general formula (3-1), L and * represent a group having the same meaning as L and * in the general formula (3), and R ₅ is a linear or branched group having 8 to 30 carbon atoms. Represents an alkyl group, and n represents an integer of 1 to 3.

R ₅ is preferably an alkyl group having 12 to 24 carbon atoms, and more preferably an alkyl group having 16 to 24 carbon atoms. R ₅ may have a substituent, and examples of the substituent include a group having the same meaning as the substituent used in R ₁ of the general formula (2). R ₅ is preferably a linear alkyl group, and more preferably composed of only carbon atoms and hydrogen atoms.

  n is preferably 1 or 2, more preferably 1.

  Although the specific example of the copper complex compound represented by the said General formula (2) below is shown, this invention is not limited to these. * In the table indicates the bonding position of each group.

  These copper complex compounds may be used alone or in combination of two or more. The content of the copper complex compound is preferably 0.5 to 10% by mass and more preferably 1 to 8% by mass with respect to the whole toner.

[Quinacridone pigment]
The toner according to the present invention may further contain a quinacridone pigment. By including the quinacridone pigment, the quinacridone pigment has a unique π-conjugated system planar structure and a polar group such as a carbonyl group or an amino group, and is therefore oriented with respect to the copper complex compound and the colorant. It has a structure that is easy to do. Therefore, the quinacridone pigment forms a strong alignment structure between the copper complex compound and the colorant, and the plasticity of the copper complex compound and the colorant does not affect the binder resin, improving the color tone and offset property. Can be made.

  The quinacridone pigment used in the present invention is a compound represented by the following general formula (4).

In the general formula (4), R _{11 to} R ₁₈ each independently represents a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, a halogen atom, or a methoxy group. Represent.

  The quinacridone pigment used in the present invention is not particularly limited, and known quinacridone pigments as shown below can be used. Specific examples of quinacridone pigments are shown below.

(1) Dimethylquinacridone pigments; I. Pigment Red 122, etc. (2) Dichloroquinacridone pigments; I. Pigment red 202 and C.I. I. Pigment Red Red 209, etc. (3) Unsubstituted quinacridone pigments; I. Pigment Violet 19 etc. (4) A mixture or solid solution of at least two pigments selected from the above quinacridone pigments.

  Among the quinacridone pigments, C.I. I. Pigment Red 122 is preferable. The quinacridone pigment used may be in a dry state such as powder, granule or bulk, or in a water-containing state such as a wet cake or slurry.

  Although the specific example of the quinacridone pigment used by this invention is shown below, the quinacridone pigment which can be used for this invention is not limited to these.

  The addition amount of the quinacridone pigment is not particularly limited, but is more preferably 0.5 to 10% by mass, and more preferably 1 to 7% by mass with respect to the whole toner.

  Further, the ratio of the quinacridone pigment, the copper complex compound and the colorant is preferably set to a certain value or more, and the total amount of the copper complex compound and the colorant is 100 parts by mass, and the quinacridone pigment is 5 to 150 parts by mass. It is preferable. When the ratio of these compounds is within the above range, the orientation structure of the copper complex compound and the colorant is surely formed around the quinacridone pigment, and the solubility of the copper complex compound and the colorant in the resin can be suppressed. it can. In this way, by adjusting the ratio of the quinacridone pigment, the copper complex compound and the colorant, the copper complex compound and the colorant do not leak between the quinacridone pigment and an orientation structure is formed, and the free copper complex compound and the colorant are colored. Since there is no agent, these compounds do not impart plasticity to the binder resin. As a result, it is considered that the fixing separation property of the toner image is improved. On the other hand, by appropriately adjusting the amount of quinacridone pigment added, it is considered that the fixing separation property is improved and the transparency of the toner image is maintained, and the color reproducibility can be secured in a wide range.

[Release agent]
The toner according to the present invention may contain a release agent (offset preventing agent). Examples of the release agent (offset preventing agent) include hydrocarbon waxes, ester waxes, natural product waxes, and amide waxes.

  Examples of hydrocarbon waxes include low molecular weight polyethylene wax, polypropylene wax, microcrystalline wax, Fischer-Tropsch wax, and paraffin wax.

  Examples of ester waxes include behenyl behenate, ethylene glycol stearate, ethylene glycol behenate, neopentyl glycol stearate, neopentyl glycol behenate, 1,6-hexanediol stearate, 1,6 Higher fatty acids such as hexanediol behenate, glycerine stearate, glycerine behenate, pentaerythritol stearate, pentaerythritol behenate, stearyl citrate, behenyl citrate, stearyl ring acid, and behenyl ring acid Examples include esters with alcohols. These release agents can be used alone or in combination of two or more.

  Melting | fusing point of a mold release agent becomes like this. Preferably it is 40-160 degreeC, More preferably, it is 50-120 degreeC. By setting the melting point within the above range, the heat-resistant storage stability of the toner is ensured, and stable toner image formation can be performed without causing cold offset or the like even when fixing at a low temperature. Further, the content of the release agent in the toner is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass.

[Toner particle size]
The particle diameter of the toner for developing an electrostatic charge image of the present invention is preferably 3 to 8 μm in terms of the median diameter (D ₅₀ ) based on the number. In the production method described later, the particle size can be controlled by the concentration of the flocculant, the addition amount of the organic solvent, the fusing time, and further the composition of the polymer itself.

When the median diameter (D ₅₀ ) on the basis of the number is 3 to 8 μm, reproducibility of fine lines and high image quality of photographic images can be achieved, and toner consumption can be reduced when a large particle size toner is used. Can be reduced. The median diameter can be measured by, for example, “Coulter Multisizer 3” (manufactured by Beckman Coulter, Inc.).

[Average circularity of toner]
The electrostatic charge image developing toner of the present invention preferably has an average circularity represented by the following formula 1 of 0.920 to 1.000, preferably 0.940 to 0.995, from the viewpoint of improving transfer efficiency. More preferably.

  The average circularity can be measured using, for example, an average circularity measuring device “FPIA-2100” (manufactured by Sysmex Corporation).

[External additive]
The external additive used in the present invention is not particularly limited, but particles such as inorganic fine particles having a number average primary particle size of about 2 to 800 nm and organic fine particles having a number average primary particle size of about 10 to 2000 nm are preferable. The type of the external additive is not particularly limited, and examples thereof include known inorganic fine particles and organic fine particles exemplified below, and lubricants. These external additives can be used alone or in combination of two or more.

  As the inorganic fine particles, conventionally known fine particles can be used. For example, silica, titania (titanium dioxide), alumina, strontium titanate fine particles, hydrotalcite, and the like are preferable. Moreover, what hydrophobized these inorganic fine particles can also be used as needed.

  Specific examples of silica fine particles include, for example, commercially available products R-805, R-976, R-974, R-972, R-812, R-809 manufactured by Nippon Aerosil Co., Ltd., HVK-2150 manufactured by Hoechst, H-200, commercially available products TS-720, TS-530, TS-610, H-5, MS-5 and the like manufactured by Cabot Corporation can be mentioned.

  As titania fine particles, for example, commercially available products T-805 and T-604 manufactured by Nippon Aerosil Co., Ltd., commercially available products MT-100S, MT-100B, MT-500BS, MT-600, MT-600SS manufactured by Teika Corporation, JA-1, commercial products manufactured by Fuji Titanium Industry Co., Ltd. TA-300SI, TA-500, TAF-130, TAF-510, TAF-510T, commercial products IT-S, IT-OA, IT manufactured by Idemitsu Kosan Co., Ltd. -OB, IT-OC, etc. are mentioned.

  Examples of the alumina fine particles include commercial products RFY-C and C-604 manufactured by Nippon Aerosil Co., Ltd., and commercial products TTO-55 manufactured by Ishihara Sangyo Co., Ltd.

  As the organic fine particles, specifically, homopolymers such as styrene and methyl methacrylate and copolymers thereof can be used.

  Further, it is possible to use a lubricant to further improve the cleaning property and the transfer property. For example, there are metal salts of higher fatty acids as follows. That is, salts of zinc stearate, aluminum, copper, magnesium, calcium, etc., zinc oleate, salts of manganese, iron, copper, magnesium, etc., zinc palmitate, salts of copper, magnesium, calcium, etc., linoleic acid And salts of zinc and calcium of ricinoleic acid.

  The addition amount of these external additives and lubricants is preferably 0.1 to 10.0 parts by mass with respect to 100 parts by mass of the toner.

[Developer]
The electrostatic image developing toner of the present invention can be used as a magnetic or non-magnetic one-component developer, but it is used as a two-component developer toner (two-component developer) mixed with a carrier. Also good. When the electrostatic image developing toner of the present invention is used as a one-component developer, a magnetic one-component developer containing non-magnetic one-component developer or about 0.1 to 0.5 μm magnetic particles in the toner. Any developer can be used, and any of them can be used. In addition, when the toner for developing an electrostatic charge image of the present invention is used as a two-component developer, examples of carriers include metals such as iron, ferrite, and magnetite, alloys of these metals with metals such as aluminum and lead, and the like. Magnetic particles made of conventionally known materials can be used, and ferrite particles are particularly preferable.

  As the coating resin constituting the coat carrier, those showing a positive charge relative to the toner are preferable. For example, olefin resin, styrene resin, acrylic resin, styrene-acrylic resin, silicone resin, ester resin, fluorine-containing polymer Resin etc. are mentioned. Moreover, as resin which comprises a resin dispersion type carrier, it is not specifically limited, A well-known thing can be used, For example, acrylic resin, a styrene-acrylic resin, a polyester resin, a fluororesin, a phenol resin etc. are used. Can do.

  A preferable carrier is a coated carrier coated with an acrylic resin as a coating resin from the viewpoint of preventing the external additive from detaching and durability.

The carrier preferably has a volume-based median diameter (D ₅₀ ) of 20 to 100 μm, more preferably 25 to 80 μm. The median diameter (D ₅₀ ) based on the volume of the carrier can be typically measured by a laser diffraction particle size distribution measuring apparatus “HELOS” (manufactured by SYMPATEC) equipped with a wet disperser. it can.

[Method for producing toner for developing electrostatic image]
Next, a method for producing an electrostatic charge image developing toner according to the present invention will be described. The method for producing the toner for developing an electrostatic charge image according to the present invention is not particularly limited, and is a pulverization method, suspension polymerization method, miniemulsion polymerization aggregation method, emulsion polymerization aggregation method, dissolution suspension method, polyester molecular elongation. And other known methods. Among these, the miniemulsion polymerization aggregation method is preferable.

  In the miniemulsion polymerization aggregation method, a polymerizable monomer solution in which wax is dissolved in an aqueous medium in which a surfactant is dissolved so as to have a concentration equal to or lower than the critical micelle concentration, and 10 to 1000 nm using mechanical energy. A dispersion liquid in which oil droplets are formed is prepared. A water-soluble radical polymerization initiator is added to the obtained dispersion to perform polymerization, thereby forming binder resin particles. Then, the formed binder resin particles are aggregated and the particles are fused to produce toner particles.

  The reason why the mini-emulsion polymerization aggregation method is preferable is that the polymerization is performed in oil droplets, so that the wax particles can be surely included in the binder resin in the toner particles.

  In the miniemulsion polymerization aggregation method, instead of adding the water-soluble radical polymerization initiator described above, an oil-soluble radical polymerization initiator is added to the monomer solution described above together with the water-soluble radical polymerization initiator. Polymerization can also be performed.

  As a method for producing a toner according to the present invention, when resin particles are formed by a miniemulsion polymerization aggregation method, resin particles having a structure of two or more layers made of binder resins having different compositions can be formed. In this case, a polymerization initiator and a polymerizable monomer are added to the dispersion of the first resin particles prepared by a conventional miniemulsion polymerization process (first stage polymerization), and the system is polymerized (second stage polymerization). ) In this way, resin particles having a two-layer structure can be formed. And the resin particle of a multilayered structure can be formed by repeating this 2nd step polymerization.

The toner production method by the miniemulsion polymerization aggregation method is performed by the following procedure, for example. That is,
(1) Dissolving / dispersing step of preparing a polymerizable monomer solution by dissolving or dispersing a releasing agent and, if necessary, a toner particle constituent material such as a charge control agent in a polymerizable monomer serving as a binder resin. (2) Dispersion preparing step of dispersing a colorant and a copper complex compound in an aqueous medium to prepare a colorant dispersion and a copper complex compound dispersion (3) The polymerizable monomer solution in an aqueous medium (4) Aggregating particles obtained by agglomerating and fusing the binder resin particles, the colorant, and the copper complex compound in an aqueous medium. (5) Aging process for adjusting the shape by aging the aggregated particles with thermal energy to produce a toner particle dispersion (6) Cooling process for cooling the toner particle dispersion (7) Cooling From toner particle dispersion Filtration and washing step for separating the toner particles into solid and liquid and removing surfactants from the toner particle surface (8) Drying step for drying the washed toner particles (9) External addition to the dried toner particles External processing step of adding an agent.

  Hereinafter, each process mentioned above is demonstrated.

(1) Dissolution / Dispersion Step This step is a step of preparing a polymerizable monomer solution by dissolving or dispersing toner particle constituent materials such as a release agent and a colorant in the polymerizable monomer.

  In this polymerizable monomer solution, it is possible to add at least one of a polymerization initiator described later and other oil-soluble components.

(2) Dispersion Preparation Step In this dispersion preparation step, the aforementioned colorant, copper complex compound, and, if necessary, quinacridone pigment are dispersed in an aqueous medium, a colorant dispersion, a copper complex compound dispersion, and This is a step of preparing quinacridone pigment dispersions as necessary.

  These colorant dispersions and the like can be prepared by dispersing a colorant or the like in an aqueous medium. The dispersion treatment of the colorant is performed in a state where the surfactant concentration is set to a critical micelle concentration (CMC) or more in water. The disperser used for the dispersion treatment of the colorant is not particularly limited, and is a medium type such as an ultrasonic disperser, a mechanical homogenizer, a pressure disperser such as a manton gourin or a pressure homogenizer, a sand grinder, a Getzmann mill, a diamond fine mill, or the like. A disperser can be used.

  As the colorant, a surface-modified one can be used. Specifically, a colorant is dispersed in a solvent, and a reaction treatment is performed by adding a surface modifier to the dispersion and raising the temperature of the system. After completion of the reaction, the colorant is filtered off, washed and filtered with the same solvent, and then dried to obtain the colorant treated with the surface modifier.

(3) Polymerization step This polymerization step is a step of forming binder resin particles containing a release agent and a binder resin. In the polymerization step, for example, the polymerizable monomer solution is added to an aqueous medium containing a surfactant having a concentration equal to or lower than the critical micelle concentration, mechanical energy is added to form oil droplets, and then water-soluble By adding a radical polymerization initiator, the polymerization reaction is carried out in the oil droplets. In addition, when forming the resin particle of a multilayer structure, it can form by adding the resin particle used as a nucleus particle in an aqueous medium, and performing a polymerization reaction.

  The binder resin particles formed in the polymerization step may be colored or uncolored. The colored binder resin particles are formed by polymerizing a monomer composition containing a colorant. In addition, when forming non-colored binder resin particles, a colorant dispersion, a copper complex compound dispersion, and, if necessary, a quinacridone pigment dispersion in the binder resin particle dispersion in the aggregation step described later. The toner particles can be formed by adding and aggregating the binder resin particles and the colorant.

  Here, the “aqueous medium” means that the main component (50% by mass or more) is made of water. That is, it refers to a dispersion medium composed of 50 to 100% by mass of water and 0 to 50% by mass of a water-soluble organic solvent. Examples of water-soluble organic solvents that are components other than water include the following. For example, there are methanol, ethanol, isopropanol, butanol, acetone, methyl ethyl ketone, tetrahydrofuran and the like. Among these, alcohol-based organic solvents such as methanol, ethanol, isopropanol, and butanol that do not dissolve the resin are particularly preferable.

  The method for dispersing the polymerizable monomer solution in the aqueous medium is not particularly limited, but a method of dispersing by adding mechanical energy is preferred. A dispersion apparatus for dispersing oil droplets by applying mechanical energy is not particularly limited. For example, “CLEAMIX (registered trademark)”, an ultrasonic disperser, a mechanical homogenizer, a manton gourin, and a pressure homogenizer Etc. Moreover, 10-1000 nm is preferable and, as for the dispersed particle diameter of a polymerizable monomer solution, 30-300 nm is more preferable.

(4) Aggregation / fusion process In the aggregation / fusion process, the binder resin particles formed in the polymerization process are aggregated and fused in an aqueous medium. In the agglomeration / fusion process, if the binder resin particle dispersion is not colored, a colorant dispersion, a copper complex compound dispersion, and, if necessary, a quinacridone pigment dispersion By adding, the binder resin particles and the colorant are aggregated and fused. In the middle of this agglomeration / fusion process, binder resin particles having different resin compositions, for example, a styrene acrylic resin dispersion containing 10 to 20% by mass of constituent units derived from methacrylic acid are added to agglomerate It is also possible to perform.

  Further, in the aggregation / fusion step, it is possible to add internal additive particles such as a charge control agent together with the binder resin particles and the colorant to cause aggregation and fusion.

  A preferred agglomeration / fusion method is to add a coagulant composed of an alkali metal salt, an alkaline earth metal salt, or the like into an aqueous medium in which binder resin particles and a colorant are present, so that these particles are added. Agglomerate. Next, the fusion resin is heated to a temperature equal to or higher than the glass transition temperature of the binder resin particles and equal to or higher than the melting peak temperature of the release agent, and the fusion proceeds simultaneously with the aggregation.

  In this aggregation / fusion process, it is necessary to quickly raise the temperature by heating, and the temperature raising rate is preferably 1 ° C./min or more. The upper limit of the rate of temperature increase is not particularly limited, but coarse particles may be generated due to rapid agglomeration and fusion, so that it is preferably 15 ° C./min or less from the viewpoint of suppressing this.

  Furthermore, after the dispersion liquid of the binder resin particles and the colorant reaches a temperature not lower than the glass transition temperature and not lower than the melting peak temperature of the release agent, the temperature of the dispersion liquid is maintained for a certain time, thereby aggregating and fusing. It is important to continue wearing. In this way, by maintaining the dispersion temperature for a certain period of time, toner particle growth (aggregation of binder resin particles and colorant) and fusion (disappearance at the interface between the particles) proceed effectively and finally. The durability of the obtained toner can be improved.

(5) Aging process Specifically, this aging process is carried out by heating and stirring the system containing the aggregated particles, so that the heating temperature, the stirring speed, and the heating time are changed until the aggregated particles have a desired average circularity. This is a step of controlling and adjusting to form toner particles having a desired shape. In this aging step, it is preferable to control the shape of the toner particles by thermal energy (heating).

  In this ripening step, a binder resin particle dispersion is further added to the toner particle dispersion to attach and fuse the binder resin particles to the surface of the toner particles, thereby forming toner particles called a so-called core-shell structure. It is good also as what to do. In this case, it is preferable that the glass transition point of the binder resin particles forming the shell be 20 ° C. or more higher than the glass transition point of the binder resin particles constituting the core.

  In addition, the binder resin particles used in the aggregation / fusion process are a resin (hydrophilic resin) made of a polymerizable monomer having an ionic dissociation group as a raw material and a polymerizable monomer having no ionic dissociation group In the case where it is configured to contain only a resin (hydrophobic resin) made from only the raw material, in this aging step, the hydrophilic resin is oriented on the surface side of the aggregated particles, and the hydrophobic resin is oriented on the inside side of the aggregated particles. Toner particles having a core-shell structure can be formed.

(6) Cooling step This cooling step is a step of cooling the toner particle dispersion. The cooling rate during the cooling treatment is preferably 1 to 20 ° C./min. The cooling treatment method is not particularly limited, and examples thereof include known methods such as a method of cooling by introducing a refrigerant from the outside of the reaction vessel, and a method of cooling by directly introducing cold water into the reaction system.

(7) Filtration / washing step In this filtration / washing step, a filtration step of separating the toner particles from the toner particle dispersion that has been cooled to a predetermined temperature in the cooling step, followed by filtration, and toner particles called wet cake It comprises a washing step of removing deposits such as surfactants and aggregating agents, alkali agents used in the aging step, and the like from the surface of the toner particles that have been filtered and processed in the form of aggregates.

  In the washing step, water washing is performed until the electrical conductivity of the filtrate reaches a level of 5 to 10 μS / cm. In the filtration step, solid-liquid separation is performed by a known filtration method such as a centrifugal separation method, a vacuum filtration method using Nutsche or the like, or a filtration method using a filter press or the like.

(8) Drying Step This drying step is a step of drying the wet cake that has been subjected to the cleaning treatment to produce dried toner particles. Dryers used in this process include spray dryers, vacuum freeze dryers, vacuum dryers, etc., stationary shelf dryers, mobile shelf dryers, fluidized bed dryers, rotary dryers, stirring dryers A machine or the like can also be used. The moisture content of the dried toner particles is preferably 5% by mass or less, and more preferably 2% by mass or less. In addition, when the toner particles that have been dried are aggregated due to weak interparticle attraction, the aggregate may be crushed. Examples of the crushing treatment apparatus include mechanical crushing apparatuses such as a jet mill, a Henschel mixer, a coffee mill, and a food processor.

(9) External Addition Processing Step This step is a step of adding an external additive to the dried toner particles as necessary. As a mixing device for adding an external additive, there is a mechanical mixing device such as a Henschel mixer or a coffee mill.

  Through the above procedure, the toner according to the present invention can be produced by the miniemulsion polymerization aggregation method.

  Hereinafter, the surfactant and the flocculant used in the toner production method by the polymerization method such as the mini-emulsion polymerization aggregation method described above will be described.

[Surfactant]
When the toner according to the present invention is produced by the suspension polymerization method or the above-described miniemulsion polymerization aggregation method or emulsion polymerization aggregation method, a surfactant is added to an aqueous medium to produce a binder resin or aggregated particles. The surfactant used in these polymerization methods is not particularly limited, but the following ionic surfactants are preferable.

(1) Sulfonate salt; sodium dodecylbenzene sulfonate, sodium arylalkyl polyether sulfonate (2) sulfate ester salt; sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium lauryl sulfate, etc. (3) Fatty acid salt; sodium oleate, sodium laurate, sodium caprate, sodium caprylate, sodium caproate, potassium stearate, calcium oleate, etc. Nonionic surfactants listed below can also be used. That is, polyethylene oxide, polypropylene oxide, a combination of polypropylene oxide and polyethylene oxide, ester of polyethylene glycol and higher fatty acid, alkylphenol polyethylene oxide, ester of higher fatty acid and polyethylene glycol, ester of higher fatty acid and polypropylene oxide, Sorbitan ester etc.

[Flocculant]
When the toner according to the present invention is produced by the miniemulsion polymerization aggregation method or the emulsion polymerization aggregation method, an aggregating agent is used for aggregating the resin particles. Examples of the flocculant include alkali metal salts and alkaline earth metal salts. Examples of the alkali metal that constitutes the flocculant include lithium, potassium, and sodium, and examples of the alkaline earth metal that constitutes the flocculant include magnesium, calcium, strontium, and barium. Of these, potassium, sodium, magnesium, calcium, and barium are preferable. Examples of the counter ion (anion constituting the salt) of the alkali metal or alkaline earth metal include a chloride ion, a bromide ion, an iodide ion, a carbonate ion, and a sulfate ion.

  Examples of the present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

(Example 1: Preparation of toner [1])
(1) Preparation of styrene acrylic resin fine particle dispersion (dispersion of binder resin fine particles [A]) (1-1) First stage polymerization A stirrer, temperature sensor, temperature controller, cooling pipe, and nitrogen introducing device An anionic surfactant solution in which 2.0 parts by mass of an anionic surfactant “sodium lauryl sulfate” was previously dissolved in 2900 parts by mass of ion-exchanged water was charged into the attached reaction vessel at a stirring speed of 230 rpm under a nitrogen stream. The internal temperature was raised to 80 ° C. while stirring.

After adding 9.0 parts by mass of a polymerization initiator “potassium persulfate (KPS)” to this anionic surfactant solution and adjusting the internal temperature to 78 ° C.,
Styrene 540 parts by mass n-butyl acrylate 154 parts by mass Methacrylic acid 63 parts by mass n-Octyl mercaptan 17 parts by mass A monomer solution [1] was added dropwise over 3 hours. After completion of the dropping, polymerization (first stage polymerization) was performed by heating and stirring at 78 ° C. for 1 hour to prepare a dispersion of “resin fine particles [a1]”.

(1-2) Second stage polymerization: formation of an intermediate layer In a flask equipped with a stirrer,
Styrene 94 parts by mass n-butyl acrylate 27 parts by mass Methacrylic acid 6 parts by mass n-octyl mercaptan 1.7 parts by mass Paraffin wax (melting point: 73 ° C.) 51 parts by mass is added as an anti-offset agent, and 85 The monomer solution [2] was prepared by heating to ° C and dissolving.

  On the other hand, a surfactant solution in which 2 parts by mass of the anionic surfactant “sodium lauryl sulfate” was dissolved in 1100 parts by mass of ion-exchanged water was heated to 90 ° C. After adding 28 parts by mass of the above-mentioned dispersion of “resin fine particles [a1]” to the surfactant solution in terms of solid content of the resin fine particles [a1], a mechanical disperser “CLEAMIX (registered) having a circulation path” is added. (Trademark) ”(manufactured by M Technique Co., Ltd.), the monomer solution [2] was mixed and dispersed for 4 hours to prepare a dispersion containing emulsified particles having a dispersed particle diameter of 350 nm. An initiator aqueous solution in which 2.5 parts by mass of potassium persulfate (KPS) is dissolved in 110 parts by mass of ion-exchanged water as a polymerization initiator is added to this dispersion, and this system is heated and stirred at 90 ° C. for 2 hours. By carrying out polymerization (second stage polymerization), a dispersion of “resin fine particles [a11]” was prepared.

(1-3) Third-stage polymerization: formation of outer layer In the above dispersion of “resin fine particles [a11]”, 2.5 parts by mass of potassium persulfate (KPS) as a polymerization initiator is added to 110 parts by mass of ion-exchanged water. Add the dissolved initiator aqueous solution, and under the temperature condition of 80 ° C,
Styrene 230 mass parts n-butyl acrylate 78 mass parts Methacrylic acid 16 mass parts n-octyl mercaptan 4.2 mass parts monomer solution [3] was dripped over 1 hour. After completion of the dropwise addition, polymerization (third stage polymerization) was performed by heating and stirring for 3 hours. Then, it cooled to 28 degreeC and produced the "dispersion liquid of binder resin microparticles | fine-particles [A]" by which binder resin microparticles | fine-particles [A] were disperse | distributed in the anionic surfactant solution.

  The binder resin fine particles [A] had a glass transition point of 45 ° C. and a softening point of 100 ° C.

(2) Preparation step of styrene acrylic modified polyester resin fine particle dispersion (dispersion of binder resin fine particles [B]) (2-1) Synthesis of styrene acrylic modified polyester resin [1] Nitrogen introduction tube, dehydration tube, stirrer And a 10 liter four-necked flask equipped with a thermocouple,
Bisphenol A propylene oxide 2-mole adduct 500 parts by mass Terephthalic acid 117 parts by mass Fumaric acid 82 parts by mass Esterification catalyst (tin octylate) 2 parts by mass were added and subjected to a polycondensation reaction at 230 ° C. for 8 hours. The reaction was performed for an hour, and the mixture was cooled to 160 ° C.

after that,
Acrylic acid 10 parts by weight Styrene 30 parts by weight Butyl acrylate 7 parts by weight Polymerization initiator (di-t-butyl peroxide) 10 parts by weight of the mixture was dropped with a dropping funnel over 1 hour, and the mixture was kept at 160 ° C. after dropping. Then, after continuing the addition polymerization reaction for 1 hour, the temperature was raised to 200 ° C. and held at 10 kPa for 1 hour, and then acrylic acid, styrene, and butyl acrylate were removed to obtain a styrene acrylic modified polyester resin [1]. Obtained.

  This styrene acrylic modified polyester resin [1] had a glass transition point of 60 ° C. and a softening point of 105 ° C.

(2-2) Preparation of styrene-acrylic modified polyester resin fine particle dispersion 100 parts by mass of the obtained styrene-acrylic modified polyester resin [1] was pulverized with “Landel mill type: RM” (manufactured by Tokuju Kogakusho Co., Ltd.). It is mixed with 638 parts by mass of a sodium lauryl sulfate solution having a concentration of 0.26% by mass prepared in advance and stirred with an ultrasonic homogenizer “US-150T” (manufactured by Nihon Seiki Seisakusho Co., Ltd.) at 30 at V-LEVEL of 300 μA. Ultrasonic dispersion was performed for minutes, and a “dispersion of binder resin fine particles [B]” in which styrene-acryl-modified polyester resin fine particles [B] having a volume-based median diameter (D ₅₀ ) of 250 nm were dispersed was produced.

(3-1) Preparation of Colorant Dispersion Liquid (1-5) An aqueous surfactant solution was prepared by stirring and dissolving 11.5 parts by mass of sodium n-dodecyl sulfate in 160 parts by mass of ion-exchanged water. To this surfactant aqueous solution, 20 parts by mass of the compound represented by the above formula (1-5) as a colorant was gradually added, and then “Cleamix (registered trademark) W motion CLM-0.8” (M -The colorant dispersion liquid (1-5) in which the particle | grains of the colorant (1-5) were disperse | distributed was prepared by carrying out a dispersion process using Technique Co., Ltd. product.

  The volume-based median diameter of the colorant particles in this colorant dispersion (1-5) was measured and found to be 221 nm.

  The volume-based median diameter is “MICROTRAC UPA-150” (manufactured by HONEYWELL), sample refractive index 1.59, sample specific gravity 1.05 (in terms of spherical particles), solvent refractive index 1.33, solvent viscosity. The measurement was performed by adjusting the zero point by introducing ion-exchanged water into the measurement cell under the measurement conditions of 0.797 (30 ° C.) and 1.002 (20 ° C.).

(3-2) Preparation of copper complex compound dispersion liquid (2-8) In place of the colorant represented by the above formula (1-5), a compound represented by the above formula (2-8) as a copper complex compound In the same manner as in the preparation of (3-1) Colorant Dispersion Liquid (1-5), except that 19.4 parts by mass of copper complex compound dispersion liquid (in which copper complex compound particles are dispersed ( 2-8) was prepared.

  About the particle diameter of the copper complex compound in this copper complex compound dispersion liquid (2-8), the volume-based median diameter is measured under the same measurement conditions as in the preparation of the above (3-1) colorant dispersion liquid (1-5). As a result, it was 181 nm.

(4) Aggregation, fusion-maturation-washing-drying-external additive addition process "Binder resin fine particles [A]" prepared in (1) above in a reaction vessel equipped with a stirrer, temperature sensor, and cooling tube The dispersion was prepared by adding 391.5 parts by mass in terms of solid content and 1700 parts by mass of ion-exchanged water, and adding 5 mol / liter sodium hydroxide aqueous solution to adjust the pH to 11.5.

Thereafter, 22 parts by mass of the colorant dispersion (1-5) was charged in terms of solid content, and then an aqueous solution in which 65 parts by mass of magnesium chloride was dissolved in 65 parts by mass of ion-exchanged water was stirred at 30 ° C. for 10 minutes. Added over time. Thereafter, the temperature was raised after standing for 3 minutes, and the temperature of the system was raised to 85 ° C. over 60 minutes, and 58.5 parts by mass of the “dispersion of binder resin fine particles [B]” in terms of the resin solid content was added. After the addition, the particle growth reaction was continued while maintaining 85 ° C. In this state, the particle diameter of the particles was measured with “Coulter Multisizer 3” (manufactured by Beckman Coulter Inc.), and when the volume-based median diameter (D ₅₀ ) reached 6.5 μm, 190 mass of sodium chloride was obtained. Particulate growth was stopped by adding an aqueous solution having a part dissolved in 760 parts by mass of ion-exchanged water. Thereafter, at 85 ° C., 38 parts by mass of the copper complex compound dispersion (2-8) as a solid content was added, and the mixture was heated and stirred as it was, so that particle fusion proceeded. -2100 "(manufactured by Sysmex Corporation) (the number of detected HPFs was 4000) and when the average circularity reached 0.945, it was cooled to 30 ° C. to obtain a“ dispersion of toner 1 ”.

  This “dispersion of toner 1” is solid-liquid separated with a centrifuge to form a wet cake of toner particles 1, and this is used until the electric conductivity of the filtrate reaches 5 μS / cm using the centrifuge. After washing with ion exchange water at 0 ° C., it was transferred to “Flash Jet Dryer” (manufactured by Seishin Enterprise Co., Ltd.) and dried until the water content became 0.6% by mass or less to obtain toner particles 1.

  1% by mass of hydrophobic silica (number average primary particle size = 12 nm) and 0.3% by mass of hydrophobic titania (number average primary particle size = 20 nm) are added to the dried toner particles 1 and mixed by a Henschel mixer. Thus, Toner 1 was produced.

(Example 2)
The amount of “dispersion of binder resin fine particles [A]” was changed to 373.5 parts by mass in terms of solid content, and the amount of “dispersion of binder resin fine particles [B]” in terms of solid content was changed to 76. Toner 2 was produced in the same manner as in Example 1 except that the content was changed to 5 parts by mass.

(Example 3)
The amount of “dispersion of binder resin fine particles [A]” was changed to 337.5 parts by mass in terms of solid content, and the amount of “dispersion of binder resin fine particles [B]” in terms of solid content was changed to 112. Toner 3 was produced in the same manner as in Example 1 except that the amount was changed to 0.5 parts by mass.

Example 4
The amount of “dispersion of binder resin fine particles [A]” was changed to 279.0 parts by mass in terms of solids, and the amount of “dispersion of binder resin fine particles [B]” in terms of solids was changed to 171. Toner 4 was produced in the same manner as in Example 1 except that the content was changed to 0.0 parts by mass.

(Example 5)
Toner 5 was produced in the same manner as in Example 3, except that the copper complex compound represented by the above formula (2-1) was used instead of the copper complex compound (2-8).

(Example 6)
Toner 6 was produced in the same manner as in Example 3, except that the copper complex compound represented by the above formula (2-12) was used instead of the copper complex compound (2-8).

(Example 7)
Toner 7 was produced in the same manner as in Example 3, except that the copper complex compound represented by the above formula (2-13) was used instead of the copper complex compound (2-8).

(Example 8)
Toner 8 was produced in the same manner as in Example 3, except that the copper complex compound represented by the above formula (2-18) was used instead of the copper complex compound (2-8).

Example 9
Toner 9 was produced in the same manner as in Example 3, except that the copper complex compound represented by the above formula (2-25) was used instead of the copper complex compound (2-8).

(Example 10)
Toner 10 was produced in the same manner as in Example 3, except that the copper complex compound represented by the formula (2-27) was used instead of the copper complex compound (2-8).

(Example 11)
Toner 11 was produced in the same manner as in Example 3, except that the copper complex compound represented by the above formula (2-34) was used instead of the copper complex compound (2-8).

(Example 12)
Toner 12 was produced in the same manner as in Example 3, except that the copper complex compound represented by the above formula (2-35) was used instead of the copper complex compound (2-8).

(Example 13)
Toner 13 was produced in the same manner as in Example 3, except that the copper complex compound represented by the above formula (2-39) was used instead of the copper complex compound (2-8).

(Example 14)
A toner 14 was produced in the same manner as in Example 3, except that the colorant represented by the above formula (1-4) was used instead of the colorant (1-5).

(Example 15)
Toner 15 was produced in the same manner as in Example 3, except that the colorant represented by the above formula (1-8) was used instead of the colorant (1-5).

(Example 16)
Toner 16 was produced in the same manner as in Example 3, except that the colorant represented by the above formula (1-14) was used instead of the colorant (1-5).

(Example 17)
Toner 17 was produced in the same manner as in Example 3, except that the colorant represented by the above formula (1-19) was used instead of the colorant (1-5).

(Example 18)
Toner 18 was produced in the same manner as in Example 3, except that the colorant represented by the above formula (1-23) was used instead of the colorant (1-5).

(Example 19)
Toner 19 was produced in the same manner as in Example 3, except that the colorant represented by the above formula (1-24) was used instead of the colorant (1-5).

(Example 20)
Toner 20 was produced in the same manner as in Example 3, except that the colorant represented by the above formula (1-25) was used instead of the colorant (1-5).

(Example 21)
Toner 21 was produced in the same manner as in Example 3, except that the colorant represented by the above formula (1-26) was used instead of the colorant (1-5).

(Example 22)
(4) A toner 22 was produced in the same manner as in Example 1 except that the aggregation, fusion-maturation-washing-drying-external additive addition step was performed as follows.

  In a reaction vessel equipped with a stirrer, a temperature sensor, and a cooling pipe, 337.5 parts by mass of "dispersion of binder resin fine particles [A]" and 1700 parts by mass of ion-exchanged water in terms of solid content are charged and 5 mol The pH was adjusted to 11.5 by adding an aqueous sodium hydroxide solution.

Thereafter, 11 parts by mass of each of the colorant dispersion (1-5) and the quinacridone pigment dispersion (4-1) containing the quinacridone pigment represented by the above formula (4-1) in terms of solid content were added. An aqueous solution obtained by dissolving 65 parts by mass of magnesium chloride in 65 parts by mass of ion-exchanged water was added over 10 minutes at 30 ° C. with stirring. Thereafter, the temperature was raised after standing for 3 minutes, and the temperature of this system was raised to 85 ° C. over 60 minutes, and 112.5 parts by mass of the “dispersion of binder resin fine particles [B]” was calculated in terms of solid content. After the addition, the particle growth reaction was continued while maintaining 85 ° C. In this state, the particle diameter of the particles was measured with “Coulter Multisizer 3” (manufactured by Beckman Coulter Inc.), and when the volume-based median diameter (D ₅₀ ) reached 6.5 μm, 190 mass of sodium chloride was obtained. Particulate growth was stopped by adding an aqueous solution having a part dissolved in 760 parts by mass of ion-exchanged water. Thereafter, 19 parts by mass of the copper complex compound dispersion (2-8) as a solid content was added at 85 ° C., and the mixture was heated and stirred as it was, so that the fusion of the particles proceeded, and the measuring device for measuring the average circularity of the toner “ FPIA-2100 ”(manufactured by Sysmex Corporation) (4000 HPF detected) was cooled to 30 ° C. when the average circularity reached 0.945, and a“ toner 22 dispersion ”was obtained. .

  This “dispersion of toner 22” is solid-liquid separated with a centrifuge to form a wet cake of toner particles, and this is used at 35 ° C. until the electrical conductivity of the filtrate reaches 5 μS / cm using the centrifuge. After that, it was transferred to “Flash Jet Dryer” (manufactured by Seishin Enterprise Co., Ltd.) and dried until the water content became 0.6% by mass or less to obtain toner particles [22].

  To the dried toner particles [22], 1% by mass of hydrophobic silica (number average primary particle size = 12 nm) and 0.3% by mass of hydrophobic titania (number average primary particle size = 20 nm) are added, and a Henschel mixer is used. By mixing, toner 22 was produced.

  The quinacridone pigment dispersion (4-1) used 20 parts by mass of the quinacridone pigment represented by the above formula (4-1) instead of the colorant represented by the above formula (1-5). Except for the above, it was prepared by the same method as the preparation of the above (3-1) colorant dispersion (1-5).

(Example 23)
In a reaction vessel equipped with a stirrer, a temperature sensor, and a cooling tube, 315.0 parts by mass of "dispersion of binder resin fine particles [A]" in terms of solid content and 1700 parts by mass of ion-exchanged water are added. The pH was adjusted to 11.5 by adding a mol / liter aqueous sodium hydroxide solution.

Thereafter, 22 parts by mass of the colorant dispersion (1-5) was added in terms of solid content, and then an aqueous solution in which 65 parts by mass of magnesium chloride was dissolved in 65 parts by mass of ion-exchanged water was stirred at 30 ° C. for 10 minutes. Added over time. Thereafter, the temperature was raised after standing for 3 minutes, and the temperature of the system was raised to 85 ° C. over 60 minutes. The dispersion of the binder resin fine particles [C] prepared by the following method was 22.5 in solid content. Next, 112.5 parts by mass of the “dispersion of the binder resin fine particles [B]” in terms of solid content was added, and then the particle growth reaction was continued while maintaining 85 ° C. In this state, the particle diameter of the particles was measured with “Coulter Multisizer 3” (manufactured by Beckman Coulter Inc.), and when the volume-based median diameter (D ₅₀ ) reached 6.5 μm, 190 mass of sodium chloride was obtained. Particulate growth was stopped by adding an aqueous solution having a part dissolved in 760 parts by mass of ion-exchanged water. Thereafter, 38 parts by mass of the copper complex compound dispersion liquid (2-8) in terms of solid content is added at 85 ° C., and the mixture is heated and stirred as it is, so that the fusion of the particles proceeds, and an average circularity measuring apparatus for toner. Using “FPIA-2100” (manufactured by Sysmex Corporation) (HPF detection number is 4000), when the average circularity reaches 0.945, the temperature is cooled to 30 ° C. to obtain a “toner 23 dispersion”. It was.

  This “dispersion of toner 23” is solid-liquid separated with a centrifuge to form a wet cake of toner particles, and this is used at 35 ° C. until the electrical conductivity of the filtrate reaches 5 μS / cm using the centrifuge. After that, it was transferred to “Flash Jet Dryer” (manufactured by Seishin Enterprise Co., Ltd.), and dried until the water content became 0.6% by mass or less to obtain toner particles [23].

  1% by mass of hydrophobic silica (number average primary particle size = 12 nm) and 0.3% by mass of hydrophobic titania (number average primary particle size = 20 nm) are added to the dried toner particles [23], and a Henschel mixer is used. The toner 23 was produced by mixing.

(Preparation of dispersion of binder resin fine particles [C])
Surfactant solution in which 2.0 parts by mass of sodium polyoxyethylene (2) dodecyl ether sulfate is dissolved in 3000 parts by mass of ion-exchanged water in a reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introduction device The internal temperature was raised to 80 ° C. while stirring at a stirring speed of 230 rpm under a nitrogen stream.

To this surfactant solution, an initiator solution prepared by dissolving 10 parts by mass of a polymerization initiator (potassium persulfate: potassium peroxydisulfate) in 200 parts by mass of ion-exchanged water is added, and the following compound is mixed. The monomer mixed solution was added dropwise over 3 hours. The polymerizable monomer mixed solution is
Styrene 528 parts by mass n-butyl acrylate 176 parts by mass Methacrylic acid 120 parts by mass n-octyl mercaptan 15 parts by mass After dropwise addition of the polymerizable monomer mixed solution, the system was heated at 80 ° C. for 1 hour and stirred to perform polymerization, and the binder resin fine particles [C] in which the binder resin fine particles [C] were dispersed were obtained. ] Was prepared.

  The glass transition point of the binder resin fine particles [C] was 61 ° C.

(Example 24)
The amount of “dispersion of binder resin fine particles [A]” used is 292.5 parts by mass in terms of solids, and the amount of “dispersion of binder resin fine particles [B]” is 112.5 masses in terms of solids. The toner 24 was produced in the same manner as in Example 23 except that the amount of the binder and the amount of the “dispersion of the binder resin fine particles [C]” were changed to 45.0 parts by mass in terms of solid content.

(Example 25)
270.0 parts by mass of "dispersion of binder resin fine particles [A]" in terms of solid content, and 112.5 mass of "dispersion of binder resin fine particles [B]" in terms of solids. The toner 25 was produced in the same manner as in Example 23, except that the amount of the binder and the amount of the “dispersion of the binder resin fine particles [C]” were changed to 67.5 parts by mass in terms of solid content.

(Example 26)
270.0 parts by mass of “dispersion of binder resin fine particles [A]” in terms of solid content, and 135.0 masses of “dispersion of binder resin fine particles [B]” in terms of solids And the amount of “dispersion of binder resin fine particles [C]” was changed to 45.0 parts by mass in terms of solid content. Moreover, the colorant (1-23) was used instead of the colorant (1-5), and the copper complex compound (2-12) was used instead of the copper complex compound (2-8). Except for these, toner 26 was produced in the same manner as in Example 23.

(Example 27)
(4) Toner 27 was produced in the same manner as in Example 1 except that the aggregation, fusion-maturation-washing-drying-external additive addition step was performed as follows.

  In a reaction vessel equipped with a stirrer, a temperature sensor, and a cooling tube, 292.5 parts by mass of "dispersion of binder resin fine particles [A]" and 1700 parts by mass of ion-exchanged water are added in terms of solid content. The pH was adjusted to 11.5 by adding a mol / liter aqueous sodium hydroxide solution.

Thereafter, 11 parts by mass of the colorant dispersion (1-5) and the quinacridone pigment dispersion (4-1) were respectively added in terms of solid content, and then 65 parts by mass of magnesium chloride was dissolved in 65 parts by mass of ion-exchanged water. The aqueous solution was added over 10 minutes at 30 ° C. with stirring. Thereafter, the temperature was raised after standing for 3 minutes, and the temperature of the system was raised to 85 ° C. over 60 minutes, and 45.0 parts by mass of the dispersion of the binder resin fine particles [C] was added in solids, After adding 112.5 parts by mass of the “resin dispersion of binder resin fine particles [B]” as the resin solid content, the particle growth reaction was continued while maintaining 85 ° C. In this state, the particle diameter of the particles was measured with “Coulter Multisizer 3” (manufactured by Beckman Coulter Inc.), and when the volume-based median diameter (D ₅₀ ) reached 6.5 μm, 190 mass of sodium chloride was obtained. Particulate growth was stopped by adding an aqueous solution in which 760 parts by mass of ion-exchanged water was dissolved. Thereafter, 19 parts by mass of the copper complex compound dispersion (2-8) as a solid content was added at 85 ° C., and the mixture was heated and stirred as it was, so that the fusion of the particles proceeded, and the measuring device for measuring the average circularity of the toner “ Using FPIA-2100 (manufactured by Sysmex Corporation) (4000 HPF detection number), when the average circularity reached 0.945, the temperature was cooled to 30 ° C., and the “dispersion of toner [27]” Obtained.

  This “dispersion of toner [27]” is solid-liquid separated with a centrifuge to form a wet cake of toner particles, and this is used until the electric conductivity of the filtrate reaches 5 μS / cm using the centrifuge. After washing with ion-exchanged water at 35 ° C., it was transferred to “Flash Jet Dryer” (manufactured by Seishin Enterprise Co., Ltd.) and dried until the water content became 0.6% by mass or less to obtain toner particles [27].

  1% by mass of hydrophobic silica (number average primary particle size = 12 nm) and 0.3% by mass of hydrophobic titania (number average primary particle size = 20 nm) are added to the dried toner particles [27], and a Henschel mixer is used. Toner 27 was produced by mixing.

(Comparative Example 1)
The amount of the "dispersion of the binder resin fine particles [A]" was changed to 450.0 parts by mass in terms of solid content, and the "dispersion of the binder resin fine particles [B]" was not used. In the same manner as in Example 1, Toner A was produced.

(Comparative Example 2)
The amount of “dispersion of binder resin fine particles [A]” was changed to 414.0 parts by mass in terms of solid content, and the amount of “dispersion of binder resin fine particles [B]” in terms of solid content was changed to 36. Toner B was produced in the same manner as in Example 1 except that the content was changed to 0.0 parts by mass.

(Comparative Example 3)
The amount of “dispersion of binder resin fine particles [A]” was changed to 261.0 parts by mass in terms of solid content, and the amount of “dispersion of binder resin fine particles [B]” was changed to 189 in terms of solid content. Toner C was produced in the same manner as in Example 1 except that the amount was changed to 0.0 parts by mass.

(Comparative Example 4)
Toner D was produced in the same manner as in Example 3, except that a colorant represented by the following formula (1-A) was used instead of the colorant (1-5).

(Comparative Example 5)
Toner E was produced in the same manner as in Example 3, except that a colorant represented by the following formula (1-B) was used instead of the colorant (1-5).

(Comparative Example 6)
Toner F was produced in the same manner as in Example 3, except that a colorant represented by the following formula (1-C) was used instead of the colorant (1-5).

(Comparative Example 7)
Toner G was produced in the same manner as in Example 3, except that a colorant represented by the following formula (1-D) was used instead of the colorant (1-5).

(Comparative Example 8)
As described below, toner H was prepared according to the method described in JP2010-2888A.

(1) Preparation of Colorant Dispersion Solution An aqueous surfactant solution was prepared by adding 7.0 parts by mass of sodium n-dodecyl sulfate to 160 parts by mass of ion-exchanged water and dissolving with stirring. 20 parts by weight of the colorant represented by the above formula (1-1) is gradually added to this surfactant aqueous solution, and then “CLEAMIX (registered trademark) W motion CLM-0.8 (M Technique Co., Ltd.). Manufactured product) ”to prepare a“ colorant dispersion H ”.

The volume-based median diameter of the particles of “Colorant Dispersion Liquid H” was measured and found to be 292 nm. The volume-based median diameter of the colorant was calculated under the following measurement conditions using “MICROTRAC UPA-150 (manufactured by HONEYWELL)”. The measurement conditions are
Sample refractive index: 1.59
Sample specific gravity: 1.05 (in terms of spherical particles)
Solvent refractive index: 1.33
Solvent viscosity: 0.797 (30 ° C) and 1.002 (20 ° C)
0 point adjustment: Adjustment was made by introducing ion exchange water into the measurement cell.

(2) Preparation of Copper Complex Compound Dispersion In the preparation of the above (1) colorant dispersion, 20 parts by mass of the copper complex compound represented by the following chemical formula (B) is used instead of the colorant (1-1). Except for the above, a copper complex compound dispersion was prepared by the same procedure. The volume-based median diameter of the copper complex compound particles in the copper complex compound dispersion was 320 nm.

(3) Preparation of quinacridone pigment dispersion In the preparation of the above (1) colorant dispersion, 8 parts by mass of the quinacridone pigment represented by the above formula (4-1) is used instead of the colorant (1-1). Except for the above, a quinacridone pigment dispersion was prepared by the same procedure. The volume-based median diameter of the quinacridone pigment in the quinacridone pigment dispersion was 222 nm.

Preparation of toner particles (1) Preparation of “resin particles H” (a) First stage polymerization An anionic surfactant having the following structural formula in a reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introduction device A surfactant aqueous solution was prepared by dissolving 4 parts by mass of sodium dodecyl sulfate, C ₁₀ H ₂₁ (OCH ₂ CH ₂ ) ₂ SO ₃ Na in 3040 parts by mass of ion-exchanged water.

  In the surfactant aqueous solution, a polymerization initiator solution in which 10 parts by mass of potassium persulfate (KPS) was dissolved in 400 parts by mass of ion-exchanged water was added, and the liquid temperature was raised to 75 ° C. A polymerizable monomer solution was added dropwise over 1 hour.

Styrene 532 parts by weight n-butyl acrylate 200 parts by weight Methacrylic acid 68 parts by weight n-octyl mercaptan 16.4 parts by weight After dropping the polymerizable monomer solution, the polymerization reaction is carried out by heating and stirring at 75 ° C. for 2 hours. (First stage polymerization) was performed to prepare “resin particle dispersion (HH)” containing “resin particles (Hh)”. The formed “resin particles (Hh)” had a weight average molecular weight of 16,500.

(B) Second-stage polymerization Styrene 101.1 parts by mass n-butyl acrylate 62.2 parts by mass Methacrylic acid 12.3 parts by mass n-octyl mercaptan 1.75 parts by mass In a flask equipped with a stirrer, the above compound was added. The polymerizable monomer solution was prepared by charging. Thereafter, 93.8 parts by mass of paraffin wax “HNP-57 (manufactured by Nippon Seiwa Co., Ltd.)” was added, the internal temperature was increased to 90 ° C., and the wax was dissolved to dissolve the wax. A meter solution was prepared.

  On the other hand, 3 parts by weight of the anionic surfactant used in the first stage polymerization was dissolved in 1560 parts by weight of ion-exchanged water to prepare a surfactant aqueous solution, which was heated to an internal temperature of 98 ° C. To this surfactant aqueous solution, 32.8 parts by mass (in terms of solid content) of the “resin particles (Hh)” was added, and further a monomer solution containing the paraffin wax was added. After that, by using a mechanical disperser “CLEAMIX (registered trademark), manufactured by M Technique Co., Ltd.” having a circulation path, the mixture is dispersed for 8 hours to contain oil droplet particles having a dispersed particle diameter of 340 nm. An oil droplet particle dispersion was prepared.

  Next, a polymerization initiator solution in which 6 parts by mass of potassium persulfate is dissolved in 200 parts by mass of ion-exchanged water is added to the oil droplet particle dispersion, followed by heating and stirring at 98 ° C. for 12 hours to obtain a polymerization reaction (No. Two-stage polymerization) was performed. A “resin particle dispersion (HHM)” containing “resin particles (Hhm)” was produced by the polymerization reaction. The formed “resin particles (Hhm)” had a weight average molecular weight of 23,000.

(C) Third-stage polymerization A polymerization initiator solution obtained by dissolving 5.45 parts by mass of potassium persulfate in 220 parts by mass of ion-exchanged water in the “resin particle dispersion (HHM)” formed by the second-stage polymerization. Was added dropwise over a period of 1 hour under a temperature condition of 80 ° C.

Styrene 293.8 parts by mass n-butyl acrylate 154.1 parts by mass n-octyl mercaptan 7.08 parts by mass After dropwise addition of the polymerizable monomer solution, polymerization reaction is performed by heating and stirring for 2 hours (third stage polymerization). Then, it was cooled to 28 ° C. to prepare “resin particle dispersion H” containing “resin particles H”. The formed “resin particles H” had a weight average molecular weight of 26,800.

(2) Production of “toner particles H” (a) Aggregation / fusion process In a reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introducing device,
420.7 parts by mass of resin particles H (solid content conversion)
Ion-exchanged water 500 parts by weight Colorant dispersion 3.2 parts by weight (solid content conversion)
Quinacridone pigment dispersion 3.5 parts by mass (solid content conversion)
Copper complex compound dispersion 4.5 parts by mass (solid content conversion)
Was added to adjust the internal temperature to 30 ° C. while stirring, and the pH was adjusted to 10 by adding a 5 mol / liter aqueous sodium hydroxide solution.

  Next, an aqueous solution obtained by dissolving 2 parts by mass of magnesium chloride hexahydrate in 1000 parts by mass of ion-exchanged water was added over 10 minutes at 30 ° C. with stirring. After the addition, the mixture was allowed to stand for 3 minutes and then the temperature increase was started. The system was heated to 75 ° C. over 60 minutes to aggregate the particles. Subsequently, when the average particle diameter of the aggregated particles was measured with “Coulter Multisizer 3 (manufactured by Beckman Coulter Co., Ltd.) and the volume-based median diameter reached 6.5 μm, 8.2 parts by mass of sodium chloride was ion exchanged An aqueous solution dissolved in 50 parts by mass of water was added to stop particle growth.

  Further, the temperature of the liquid was set to 80 ° C., and the mixture was heated and stirred for 4 hours to continue the fusing to produce “toner particle dispersion H”. With respect to the “toner particle dispersion H”, the average circularity of the toner particles was measured using “FPIA2100 (manufactured by Sysmex Corporation)” and found to be 0.940.

(B) Washing / Drying Step Next, the produced “toner particle dispersion H” was filtered, and the washing treatment was repeated using ion-exchanged water at 45 ° C. After completion of the cleaning treatment, drying treatment was performed with hot air at 40 ° C. to produce “toner particles H” having a volume-based median diameter of 6.2 μm.

(3) External Addition Treatment To the produced “toner particle H”, as an external additive, 0.6 parts by mass of hexamethylsilazane-treated silica (average primary particle size 12 nm) and n-octylsilane-treated titanium dioxide ( 0.8 parts by mass of average primary particle size 24 nm) was added. The external addition process was performed by using “Henschel mixer (manufactured by Mitsui Miike Seisakusho Co., Ltd.)” and mixing under the conditions of a peripheral speed of a stirring blade of 35 m / second, a processing temperature of 35 ° C., and a processing time of 15 minutes. In this way, Toner H was produced. The produced “Toner H” had no change in shape and particle size before and after the external addition process.

≪Evaluation≫
《Saturation change range》
Using “bizhub PRO C6500 (manufactured by Konica Minolta Business Technologies Co., Ltd.)”, a test chart for color gamut measurement is output in the default mode, and the output test chart for color gamut measurement is “Spectrolina / Scan Bundle (Gretag Macbeth). ). The color gamut was measured under the following conditions.

Measurement conditions Light source: D50 light source Observation field: 2 °
Concentration: ANSI T
White standard: Abs
Filter: UV Cut
Measurement mode: Reflectance Language: Japan
For the evaluation of color gamut measurement, solid images (2 cm × 2 cm) of magenta single color (M) are produced. This solid image is measured under the above-described measurement conditions, expressed in La−a ^* −b ^* coordinates, and saturation is obtained from the value. The fixing temperature was 185 ° C. and 160 ° C., and the value obtained by subtracting the saturation at 160 ° C. from the saturation at 185 ° C. was defined as the change range of the saturation. The change width of the saturation was 1.5 or less, and 1.0 or less was good among them.

<Toner particle size distribution>
Measurement and calculation are performed using a device in which a computer system (Beckman Coulter, Inc.) equipped with data processing software “Software V3.51” is connected to Coulter Counter Multisizer 3 (Beckman Coulter, Inc.).

  As a measurement procedure, 0.02 g of toner is blended with 20 ml of a surfactant solution (for example, a surfactant solution obtained by diluting a neutral detergent containing a surfactant component 10 times with pure water for the purpose of dispersing the toner). After that, ultrasonic dispersion is performed for 1 minute to prepare a toner dispersion. This toner dispersion is injected into a beaker containing ISOTON II (manufactured by Beckman Coulter, Inc.) in a sample stand with a pipette until the display density of the measuring instrument becomes 5% to 10%. By setting this concentration range, a reproducible measurement value can be obtained. In the measuring machine, the measurement is performed with the measurement particle count set to 25000 and the aperture diameter set to 100 μm.

  The coefficient of variation of the particle size distribution measured by the above method was ranked according to the following.

A: Less than 19% B: 19% or more and less than 22% Δ: 22% or more and less than 25% ×: 25% or more.

  The evaluation results are shown in Table 1 below.

  As is apparent from Table 1 above, the toners of Examples 1 to 27, which are toners for developing electrostatic images according to the present invention, are excellent in color reproducibility even when the fixing temperature varies, and the toner particle size distribution is narrow. I understood that. In particular, a toner further containing a styrene acrylic resin having a constituent unit derived from methacrylic acid of 10 to 20% by mass as the binder resin has a smaller chroma change width and is further excellent in color reproducibility. I understood.

Claims (2)

Binder resin including styrene acrylic resin and styrene acrylic modified polyester resin,
A colorant represented by the following general formula (1), and a copper complex compound represented by the following general formula (2),
Including at least
The electrostatic image developing toner, wherein the content of the styrene acrylic modified polyester resin is 10 to 40% by mass with respect to the total mass of the binder resin:
In the general formula (1),
Rx ₁ and Rx ₂ are each independently a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms,
Lx is a hydrogen atom or a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms,
Gx ₁ is a linear, branched, or cyclic alkyl group or unsubstituted C2-20 substituted,
Gx ₂ is a substituted or unsubstituted linear or branched alkyl group having 1 to 5 carbon atoms,
Gx ₃ is a hydrogen atom, a halogen atom, a group represented by Gx ₄ —CO—NH—, or a group represented by Gx ₅ —N (Gx ₆ ) —CO—, wherein Gx ₄ is a substituent. Gx ₅ and Gx ₆ are each independently a hydrogen atom or a substituent,
Qx ₁ , Qx ₂ , Qx ₃ , Qx ₄ , and Qx ₅ are each independently a hydrogen atom or a substituent,
In the general formula (2),
R ₁ is a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms,
R ₂ is a hydrogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfamoyl group, a sulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, a halogen atom, or a cyano group,
R ₃ is a substituted or unsubstituted aromatic hydrocarbon-containing group having 9 to 120 carbon atoms.   The styrene acrylic resin containing at least two kinds of the styrene acrylic resins, at least one of which is a styrene acrylic resin having a content of structural units derived from methacrylic acid of 10 to 20% by mass. The toner for developing an electrostatic charge image according to 1.