JP2021046477A - Manufacturing method of resin particle dispersion, manufacturing method of toner, image formation method, and, resin particle dispersion - Google Patents

Abstract

To provide a manufacturing method of a resin particle dispersion excellent in fixability and transferability of an obtained toner.SOLUTION: A manufacturing method of a resin particle dispersion comprises the steps of: melting for forming a molten mixture while giving shearing force by adding a surfactant and a basic compound to a resin mixture containing an amorphous resin and a crystalline resin in the absence of an organic solvent; and emulsification for emulsifying by adding an aqueous medium while giving shearing force to the molten mixture, in which a content of the surfactant in the molten mixture is 1 mass% or larger and 5 mass% or smaller relative to a total mass of a resin in the molten mixture, and a content of the basic compound in the molten mixture is 0.05 mole or larger and 0.2 mole or smaller relative to 1 kg of the resin in the molten mixture.SELECTED DRAWING: Figure 1

Description

The present invention relates to a method for producing a resin particle dispersion liquid, a method for producing a toner, a method for forming an image, and a resin particle dispersion liquid.

As a toner manufacturing method, the conventional kneading and pulverizing method has been changed to a wet manufacturing method in which particles are granulated in a solution or water, and the wet manufacturing method has become the mainstream. Examples of the wet production method include a suspension polymerization method, a dissolution suspension method, and an emulsion aggregation and coalescence method.

As a conventional method for producing polyester latex, the one described in Patent Document 1 is known.
Patent Document 1 describes an additive that reduces the viscosity, including a crystalline polyester resin, in the absence of an organic solvent for the formation of a resin mixture having a softening point of about 95 ° C to about 120 ° C. A step of contacting at least one non-crystalline polyester resin, a step of contacting the resin mixture with a surfactant and a neutralizing agent, a step of melting and mixing the mixture, and the melting for forming an emulsion. A method including a step of bringing the mixture into contact with deionized water and a step of continuously recovering the latex particles is disclosed.

Japanese Unexamined Patent Publication No. 2011-162784

The problem to be solved by the present invention is that only the amorphous resin is used as the resin, or the content of the surfactant in the molten mixture is 1% by mass based on the total mass of the resin in the molten mixture. Less than or more than 5% by mass, or the content of the basic compound in the melt mixture is less than 0.05 mol or more than 0.2 mol with respect to 1 kg of the resin in the melt mixture. It is an object of the present invention to provide a method for producing a resin particle dispersion liquid, which is excellent in fixability and transferability of the obtained toner.

Specific means for solving the above problems include the following aspects.
<1> A melting step of adding a surfactant and a basic compound to a resin mixture containing an amorphous resin and a crystalline resin in the absence of an organic solvent to obtain a melt mixture while imparting shearing force, and the melting step. The emulsification step of adding an aqueous medium to emulsify the mixture while applying shearing force is included, and the content of the surfactant in the molten mixture is 1% by mass or more with respect to the total mass of the resin in the molten mixture. A method for producing a resin particle dispersion, which is 5% by mass or less and the content of the basic compound in the melt mixture is 0.05 mol or more and 0.2 mol or less with respect to 1 kg of the resin in the melt mixture. ..
<2> The method for producing a resin particle dispersion according to <1>, wherein the content of the crystalline resin in the molten mixture is 2% by mass or more and 15% by mass or less with respect to the total mass of the molten mixture.
<3> The method for producing a resin particle dispersion liquid according to <1> or <2>, wherein the surfactant contains two or more kinds of surfactants.
<4> The method for producing a resin particle dispersion liquid according to <3>, wherein the two or more kinds of surfactants contain two or more kinds of anionic surfactants.
<5> The method for producing a resin particle dispersion according to <4>, wherein the two or more anionic surfactants contain an alkylbenzene sulfonate compound and a disulfonate compound having a monoalkyldiphenyl ether structure.
<6> The resin particle dispersion according to any one of <1> to <5>, wherein the content of sulfur atoms in the resin particles in the resin particle dispersion liquid is 0.03% by mass or more and 1% by mass or less. Liquid manufacturing method.
<7> The method for producing a resin particle dispersion liquid according to <6>, wherein the content of sulfur atoms in the resin particles in the resin particle dispersion liquid is 0.06% by mass or more and 0.6% by mass or less.
<8> The method according to any one of <1> to <7>, wherein the content of the alkali metal atom in the resin particles in the resin particle dispersion is 0.1% by mass or more and 1.5% by mass or less. A method for producing a resin particle dispersion.
<9> The method for producing a resin particle dispersion liquid according to <8>, wherein the content of the alkali metal atom in the resin particles in the resin particle dispersion liquid is 0.15% by mass or more and 1% by mass or less.
<10> Any of <1> to <9>, wherein the weight average molecular weight in the molecular weight distribution of the crystalline resin in the melt mixture is smaller than the weight average molecular weight of the amorphous resin in the melt mixture. The method for producing a resin particle dispersion liquid according to one of the above.
<11> The method for producing a resin particle dispersion liquid according to any one of <1> to <10>, wherein the melt mixture contains a pigment.
<12> The resin particle dispersion liquid according to any one of <1> to <11>, wherein the amorphous resin is an amorphous polyester resin and the crystalline resin is a crystalline polyester resin. Production method.
<13> The resin particles include any of <1> to <12>, including an agglomeration step of forming agglomerated particles containing resin particles and a fusion step of forming toner particles by fusing the agglomerated particles. A method for producing a toner for static charge image development containing resin particles contained in the resin particle dispersion liquid produced by the method for producing the resin particle dispersion liquid according to one of the above.
<14> The image retention by a charging step of charging the surface of the image holder, a static charge image forming step of forming a static charge image on the surface of the charged image holder, and a static charge image developer containing toner. A development step of developing an electrostatic charge image formed on the surface of the body as a toner image, a transfer step of transferring the toner image formed on the surface of the image holder to the surface of a recording medium, and a transfer step of transferring the toner image formed on the surface of the image holder to the surface of the recording medium. An image forming method comprising a fixing step of fixing a transferred toner image, wherein the toner contains a toner produced by the method for producing an electrostatic charge image developing toner according to <13>.
<15> Amorphous resin, crystalline resin, surfactant, and resin particles containing a basic compound are contained, and the content of the surfactant is 1% by mass or more based on the total mass of the resin particles. The content of the basic compound in the resin particle dispersion is 5% by mass or less, and the content of the basic compound in the resin particle dispersion is 0.05 mol or more and 0.2 mol or less with respect to 1 kg of the resin in the resin particle dispersion. The content of sulfur atoms in the above is 0.03% by mass or more and 1% by mass or less, and the content of alkali metal atoms in the resin particles is 0.1% by mass or more and 1.5% by mass or less. liquid.

According to the invention according to <1> or <11>, only the amorphous resin is used as the resin, or the content of the surfactant in the molten mixture is based on the total mass of the resin in the molten mixture. The content of the basic compound in the melt mixture is less than 0.05 mol or more than 5% by mass, or less than 0.05 mol or 0.2 with respect to 1 kg of the resin in the melt mixture. Provided is a resin particle dispersion liquid having excellent fixability and transferability of the obtained toner as compared with the case where the amount is more than molar.
According to the invention according to <2>, the content of the crystalline resin in the molten mixture is less than 2% by mass or more than 15% by mass with respect to the total mass of the molten mixture. Provided is a resin particle dispersion liquid having excellent fixability and transferability of the toner.
According to the invention according to <3>, there is provided a resin particle dispersion liquid that is superior in fixability and transferability of the obtained toner as compared with the case where only one type of the surfactant is contained.
According to the invention according to <4>, there is provided a resin particle dispersion liquid that is superior in fixability and transferability of the obtained toner as compared with the case where only one kind of the anionic surfactant is contained.
According to the invention according to <5>, as compared with the case where the anionic surfactant contains only two kinds of alkylbenzene sulfonate compounds or two kinds of disulfonate compounds having a monoalkyldiphenyl ether structure, it is obtained. Provided is a resin particle dispersion liquid having excellent fixability and transferability of the resulting toner.
According to the invention according to <6>, the obtained toner is fixed as compared with the case where the content of sulfur atoms in the resin particles in the resin particle dispersion is less than 0.03% by mass or more than 1% by mass. A resin particle dispersion having excellent properties and transferability is provided.
According to the invention according to <7>, the obtained toner is obtained as compared with the case where the content of sulfur atoms in the resin particles in the resin particle dispersion is less than 0.06% by mass or more than 0.6% by mass. A resin particle dispersion having excellent fixability and transferability is provided.
According to the invention according to <8>, it can be obtained as compared with the case where the content of the alkali metal atom in the resin particles in the resin particle dispersion is less than 0.1% by mass or more than 1.5% by mass. A resin particle dispersion having excellent toner fixability and transferability is provided.
According to the invention according to <9>, the content of the alkali metal atom in the resin particles in the resin particle dispersion is less than 0.15% by mass or more than 1% by mass, as compared with the case of the obtained toner. A resin particle dispersion having excellent fixability and transferability is provided.
According to the invention according to <10>, the weight average molecular weight of the crystalline resin in the molten mixture is larger than the weight average molecular weight of the amorphous resin in the molten mixture. A resin particle dispersion having excellent fixability and transferability of the obtained toner is provided.
According to the invention according to <12> or <13>, the resin particle dispersion is superior in the fixability and transferability of the obtained toner as compared with the case where the amorphous resin or the crystalline resin is a styrene acrylic resin. Liquid is provided. Whether only amorphous resin is used as the resin, or the content of the surfactant in the molten mixture is less than 1% by mass or more than 5% by mass with respect to the total mass of the resin in the molten mixture. Alternatively, it was produced by a method for producing a resin particle dispersion in which the content of the basic compound in the molten mixture is less than 0.05 mol or more than 0.2 mol with respect to 1 kg of the resin in the molten mixture. Provided is a method for producing a toner or a method for forming an image, which is superior in fixing property and transferability of the toner as compared with the case of using a resin particle dispersion liquid.
According to the invention according to <14>, the resin contains only an amorphous resin, or the content of the surfactant is less than 1% by mass or 5% by mass with respect to the total mass of the resin particles. Compared to the case where the content of the basic compound in the resin particle dispersion is more than 0.05 mol or more than 0.2 mol with respect to 1 kg of the resin in the resin particle dispersion. Provided is a resin particle dispersion liquid having excellent fixability and transferability of the obtained toner.

It is a schematic block diagram which shows an example of the manufacturing apparatus preferably used in the manufacturing method of the resin particle dispersion liquid which concerns on this embodiment. It is a schematic block diagram which shows the image forming apparatus which concerns on this embodiment. It is a schematic block diagram which shows the process cartridge which concerns on this embodiment.

When referring to the amount of each component in the composition in the present specification, if a plurality of substances corresponding to each component are present in the composition, the plurality of species present in the composition unless otherwise specified. Means the total amount of substances in.
In the present specification, the "toner for static charge image development" is also simply referred to as "toner", and the "static charge image developer" is also simply referred to as "developer".

Hereinafter, embodiments that are an example of the present invention will be described.

<Manufacturing method of resin particle dispersion>
In the method for producing a resin particle dispersion liquid according to the present embodiment, a surfactant and a basic compound are added to a resin mixture containing an amorphous resin and a crystalline resin in the absence of an organic solvent to impart shearing force. It includes a melting step of forming a melt mixture and an emulsification step of adding an aqueous medium to the melt mixture and emulsifying it, and the content of the surfactant in the melt mixture is the resin in the melt mixture. The content of the basic compound in the melt mixture is 0.05 mol or more and 0.2 by mass with respect to 1 kg of the resin in the melt mixture. It is less than a molar.

In the conventional method that does not use an organic solvent, a large amount of alkali metal elements in the state of ions or the like derived from the basic compound or surfactant used for emulsification and dispersion of the resin remain in the resin particles in the resin particle dispersion liquid. The present inventors have found that this is done. Further, the present inventors have stated that when resin particles in which a large amount of alkali metal elements remain are used as a raw material for a toner for static charge image development, the fixability and transferability of the toner for static charge image development may decrease. Found.
However, as a result of detailed studies by the present inventors, even in the absence of an organic solvent, an amorphous resin and a crystalline resin are used as the resin, and the surfactant in the molten mixture is used. The content is 1% by mass or more and 5% by mass or less with respect to the total mass of the resin in the molten mixture, and the content of the basic compound in the molten mixture is based on 1 kg of the resin in the molten mixture. , 0.05 mol or more and 0.2 mol or less, it was found that the obtained toner is excellent in fixability and transferability.
Although the detailed mechanism of action is unknown, a crystalline resin is added to act as a plasticizer for the amorphous resin to reduce the viscosity and reduce the amount of surfactant and basic compound required for emulsification. As a result, the amount of sulfur atoms and the amount of alkali metal ions contained in the resin particles can be reduced, the chargeability is improved, the melt viscosity of the resin mixture is lowered, and the fixability and transferability in the obtained toner are reduced. It is estimated that it is excellent.

Hereinafter, the method for producing the resin particle dispersion liquid according to the present embodiment will be described in detail.

(Melting process)
In the method for producing a resin particle dispersion liquid according to the present embodiment, a surfactant and a basic compound are added to a resin mixture containing an amorphous resin and a crystalline resin in the absence of an organic solvent to impart shearing force. However, the melt step is included, and the content of the surfactant in the melt mixture is 1% by mass or more and 5% by mass or less with respect to the total mass of the resin in the melt mixture. The content of the basic compound in the mixture is 0.05 mol or more and 0.2 mol or less with respect to 1 kg of the resin in the molten mixture.
In the melting step, one type of surfactant may be used alone, or two or more types may be used in combination. Among them, from the viewpoint of fixability and transferability in the obtained toner, the surfactant preferably contains two or more kinds of surfactants, and more preferably contains two or more kinds of anionic surfactants. As the anionic surfactant, it is more preferable to contain an alkylbenzene sulfonate compound and a disulfonate compound having an alkyldiphenyl ether structure, and as the anionic surfactant, an alkylbenzene sulfonate compound and a monoalkyldiphenyl ether structure are used. It is particularly preferable to include a disulfonate compound having.
Further, in the melting step, one type of basic substance may be used alone, or two or more types may be used in combination.

In the melting step, the content of the surfactant in the melt mixture is 1% by mass or more and 5% by mass or less with respect to the total mass of the resin in the melt mixture, and the fixability and transfer in the obtained toner. From the viewpoint of properties, it is preferably 1% by mass or more and 4% by mass or less, more preferably 1.5% by mass or more and 3.5% by mass or less, and 2.5% by mass or more and 3.5% by mass or less. Is particularly preferable. Within the above range, the emulsion dispersibility is excellent, and the toner fixability and transferability are excellent.

In the melting step, the content of the basic compound is 0.05 mol or more and 0.2 mol or less with respect to 1 kg of the resin in the molten mixture, and from the viewpoint of fixability and transferability in the obtained toner, It is preferably 0.05 mol or more and 0.18 mol or less, more preferably 0.08 mol or more and 0.15 mol or less, and particularly preferably 0.08 mol or more and 0.12 mol or less. Within the above range, the emulsion dispersibility is excellent, and the toner fixability and transferability are excellent.

In the melting step, the resin (amorphous resin and crystalline resin), the surfactant, and the basic substance are melt-mixed without using an organic solvent. The "organic solvent" in the present embodiment is an organic solvent that dissolves the resin, and is an organic solvent other than an aqueous medium such as alcohol.

The mixing temperature in the melting step is not particularly limited, but is preferably 50 ° C. to 150 ° C., more preferably 50 ° C. to 100 ° C. from the viewpoint of mixing uniformity and emulsification dispersibility in the emulsification step. preferable.
Further, the melting temperature in the melting step is preferably a temperature equal to or higher than the glass transition temperature (Tg) of the amorphous resin in order to facilitate mixing, and is a temperature of Tg + 5 ° C. or higher of the amorphous resin. Is more preferable.
The mixing means used in the melting step is not particularly limited, and a known mixing device or the like is used. Examples of the mixing device include a roll mill, a kneader, a pressurized kneader, a Bambari mixer, a lab plast mill, a uniaxial or biaxial extruder and the like.
Among them, an extruder and a kneader are preferably mentioned.

Examples of the surfactant used in the melting step include anionic surfactants, amphoteric surfactants, cationic surfactants, and various surfactants such as nonionic surfactants. Among them, an anionic surfactant is preferable, a sulfate ester type or a sulfonic acid type anionic surfactant is more preferable, and a sulfonic acid type anionic surfactant is particularly preferable, from the viewpoint of fixability and transferability in the obtained toner.

As the anionic surfactant, any type of carboxylic acid type, sulfate ester type, sulfonic acid type, and phosphoric acid ester type can be used. For example, fatty acid salts, rosinates, naphthenates, ether carboxylates, alkenyl succinates, primary alkyl sulfates, secondary alkyl sulfates, alkylpolyoxyethylene sulfates, alkylphenylpolyoxyethylene sulfates, Monoacyl glycerin sulfate, acylaminosulfate ester salt, sulfated oil, sulfated fatty acid alkyl ester, α-olefin sulfonate, secondary alkane sulfonate, α-sulfo fatty acid salt, acyl isethionate, dialkyl sulfosuccinate, Alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyldiphenyl ether disulfonate, petroleum sulfonate, lignin sulfonate, alkyl phosphate, alkyl polyoxyethylene phosphate, alkylphenyl polyoxyethylene phosphate, perfluoro Examples thereof include alkyl carboxylates, perfluoroalkyl sulfonates, and perfluoroalkyl phosphates.

An amphoteric surfactant is a surfactant having both a cationic group and an anionic group in the molecular structure, and is a substance having charge separation in the molecular structure but no charge as a whole molecule. Means.
Examples of the amphoteric ion surfactant include N-alkylnitrilotriacetic acid, N-alkyldimethylbetaine, N-alkyloxymethyl-N, N-diethylbetaine, N-alkylsulfobetaine, N-alkylhydroxysulfobetaine, and lecithin. Perfluoroalkyl sulfonamide alkyl betaine can be mentioned.

Examples of the cationic surfactant include N-acylamine salt, quaternary ammonium salt, and imidazolium salt. Specific examples thereof include fatty acid polyethylene polyamide, amide, alkyltrimethylammonium salt, and dialkyldimethylammonium salt. Alkyldimethylbenzylammonium salt, alkylpyridinium salt, acylaminoethylmethyldiethylammonium salt, acylaminopropyldimethylbenzylammonium salt, acylaminopropyldimethylhydroxyethylammonium salt, acylaminoethylpyridinium salt, diacylaminoethylammonium salt, diasiloxyethyl Examples thereof include methylhydroxyethylammonium salt, alkyloxymethylpyridinium salt, and 1-acylaminoethyl-2-alkylimidazolium salt.

Examples of the nonionic surfactant include an ester in which a polyhydric alcohol and a fatty acid are ester-bonded, an ether such as a polyoxyethylene alkyl ether or a polyoxyethylene alkyl phenyl ether, a polyoxyethylene polyoxypropylene glycol, and a fatty acid to which ethylene oxide is added. , Polyhydric alcohol fatty acid ester to which ethylene oxide is added, fatty acid alkanolamide in which a hydrophobic group and a hydrophilic group are bonded by an amide bond, and an alkyl polyglycoside.

The anionic surfactant, amphoteric surfactant, cationic surfactant and nonionic surfactant are not limited to those listed above, and in addition to the above, known anionic surfactants and amphoteric surfactants are used. Agents, cationic surfactants, nonionic surfactants and the like may be used.

Specific examples of the basic substance used in the melting step include hydroxides of alkali metals such as lithium, sodium and potassium, and oxides or hydroxides of alkaline earth metals such as magnesium and calcium. Can be mentioned. Among them, from the viewpoint of fixability and transferability in the obtained toner, alkali metal or alkaline earth metal hydroxide is preferable, alkali metal hydroxide is more preferable, and potassium hydroxide or sodium hydroxide is further preferable. Sodium hydroxide is particularly preferred.

The amorphous resin (also referred to as “non-crystalline resin”) and the crystalline resin used in the melting step are preferably binder resins for the static charge image developing toner.
The "crystallinity" of the resin means that the resin has a clear endothermic peak rather than a stepwise endothermic change in differential scanning calorimetry (DSC). Specifically, the temperature rise rate is 10 (° C.). / Min) indicates that the half-value width of the endothermic peak is within 10 ° C.
On the other hand, "amorphous" of the resin means that the half width exceeds 10 ° C., shows a stepwise endothermic amount change, or does not show a clear endothermic peak.

The amount of the crystalline resin used in the melting step is 0.5 parts by mass or more and 40 parts by mass with respect to 100 parts by mass of the total amount of the amorphous resin and the crystalline resin from the viewpoint of fixability and transferability in the obtained toner. It is preferably 1 part by mass or less, more preferably 1 part by mass or more and 30 parts by mass or less, further preferably 2 parts by mass or more and 20 parts by mass or less, and 2 parts by mass or more and 15 parts by mass or less. Is particularly preferable.

Examples of the amorphous resin and the crystalline resin include a polycondensation resin and an addition copolymer resin. For example, a polyolefin resin such as polyethylene and polypropylene, and a styrene containing polystyrene, poly (α-methylstyrene) and the like as main components. (Meta) acrylic resin containing polymethylmethacrylate, polyacrylonitrile, etc. as the main components, styrene- (meth) acrylic copolymer resin, polyamide resin, polycarbonate resin, polyether resin, polyester resin, and both of them. Polymer resin can be mentioned.
Among them, as the amorphous resin and the crystalline resin, it is preferable that the polyester resin, that is, the amorphous resin is an amorphous polyester resin, and the crystalline resin is a crystalline polyester resin.
Further, as the amorphous resin and the crystalline resin, a resin having an acid group such as a carboxylic acid group (carboxy group) or a sulfonic acid group is preferable, and a polyester resin having an acid group is more preferable. A polyester resin having a carboxy group is more preferable. In the above aspect, dispersion in an aqueous medium in the emulsification step is easier.

As the polycondensation resin, for example, a polyester resin, a polyamide resin and the like can be preferably exemplified, and in particular, a polyester resin obtained by using a polycarboxylic acid and a polyol as a polycondensation monomer. Is preferable.
Examples of the polycondensable monomer that can be used in the present embodiment include polyvalent carboxylic acid, polyol, hydroxycarboxylic acid, polyamine, or a mixture thereof. In particular, the polycondensable monomer is preferably a polyvalent carboxylic acid, a polyol, and an ester compound (oligomer and / or prepolymer) thereof, and is subjected to a direct ester reaction or a transesterification reaction. Those that obtain polyester resin are preferable.
In the present embodiment, the polycondensation resin is obtained by polycondensing at least one selected from the group consisting of polycondensable monomers, their oligomers and prepolymers, and among these, polycondensable monomers. It is preferable to use.

A polyvalent carboxylic acid is a compound containing two or more carboxy groups in one molecule. Of these, dicarboxylic acid is a compound containing two carboxy groups in one molecule, for example, oxalic acid, succinic acid, glutaric acid, maleic acid, adipic acid, β-methyladipic acid, azelaic acid, sebacic acid, Nonandicarboxylic acid, decandicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, fumaric acid, citraconic acid, diglycolic acid, cyclohexane-3,5-diene-1,2-carboxylic acid, hexahydroterephthalic acid, malonic acid, pimerin Acid, speric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, p-carboxyphenylacetic acid, p-phenylene diacetic acid, m-phenylene diacetic acid, o-phenylene diacetic acid, diphenyl Examples thereof include acetic acid, diphenyl-p, p'-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, anthracenedicarboxylic acid, cyclohexanedicarboxylic acid and the like. ..
Examples of polyvalent carboxylic acids other than dicarboxylic acid include trimellitic acid, trimesic acid, pyromellitic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, pyrentricarboxylic acid, pyrenetetracarboxylic acid, itaconic acid, and glutaconic acid. Examples thereof include n-dodecyl succinic acid, n-dodecenyl succinic acid, isododecyl succinic acid, isododecenyl succinic acid, n-octyl succinic acid, n-octenyl succinic acid, and lower esters thereof. Furthermore, these acid halides and acid anhydrides are also used.
These may be used alone or in combination of two or more.
The lower ester means that the alkoxy portion of the ester has 1 to 8 carbon atoms. Specific examples thereof include methyl ester, ethyl ester, n-propyl ester, isopropyl ester, n-butyl ester and isobutyl ester.

A polyol is a compound containing two or more hydroxy groups in one molecule. Of these, the diol is a compound containing two hydroxy groups in one molecule. Specifically, for example, as the diol, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene. Glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol , 1,11-Undecanediol, 1,12-Dodecanediol, 1,13-Tridecanediol, 1,14-Tetradecanediol, 1,18-Octadecanediol, 1,14-Eicosandecanediol, Diethylene glycol, Triethylene Glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,4-butenediol, neopentyl glycol, 1,4-cyclohexanediol , Polytetramethylene glycol, hydrogenated bisphenol A, bisphenol A, bisphenol F, bisphenol S, alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts of the bisphenols and the like. Of these, alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols are preferable, and alkylene oxide adducts of bisphenols and alkylene oxide adducts having 2 to 12 carbon atoms are particularly preferable. It is used in combination with alkylene glycol.
Further, in order to facilitate water dispersibility, for example, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolvaleric acid and the like are exemplified.

Examples of trihydric or higher alcohols include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, hexamethylol melamine, hexaethylol melamine, tetramethylol benzoguanamine, tetraethylol benzoguanamine, sorbitol, trisphenol PA, phenol novolac, and the like. Examples thereof include cresol novolac and alkylene oxide adducts of the above trivalent or higher polyphenols. These may be used alone or in combination of two or more.
Further, an amorphous resin or a crystalline resin can be easily obtained by combining these polycondensable monomers.

In addition, hydroxycarboxylic acid can also be used. Specific examples of the hydroxycarboxylic acid include hydroxyheptanic acid, hydroxyoctanoic acid, hydroxydecanoic acid, hydroxyundecanoic acid, malic acid, tartaric acid, mucilage acid, citric acid and the like.

The polyamines include ethylenediamine, diethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,4-butenediamine, and 2,2-dimethyl-1,3-butane. Examples thereof include diamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,4-cyclohexanediamine, 1,4-cyclohexanebis (methylamine) and the like.

The weight average molecular weight (Mw) of the polycondensation resin such as polyester resin is preferably 5,000 or more and 1,000,000 or less, and more preferably 7,000 or more and 500,000 or less.
The number average molecular weight (Mn) of the polycondensation resin is preferably 2,000 or more and 100,000 or less.
The molecular weight distribution Mw / Mn of the polycondensation resin is preferably 1.5 or more and 100 or less, and more preferably 2 or more and 60 or less.
The weight average molecular weight and the number average molecular weight are measured by gel permeation chromatography (GPC). The molecular weight measurement by GPC is carried out by using GPC / HLC-8120GPC manufactured by Tosoh Corporation as a measuring device, using a column / TSKgel SuperHM-M (15 cm) manufactured by Tosoh Corporation, and using a tetrahydrofuran (THF) solvent. The weight average molecular weight and the number average molecular weight are calculated from the measurement results using a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample.

The acid value of the obtained polyester resin is preferably 1 mgKOH / g or more and 50 mgKOH / g or less, and 2 mgKOH / g or more and 30 mgKOH / g or less, from the viewpoint of fixability and transferability in the obtained toner. More preferably, it is 5 mgKOH / g or more and 15 mgKOH / g or less. The first reason for this is that in order to put it into practical use as a high-quality toner, it is indispensable to control the particle size and distribution of the toner in an aqueous medium, and when the acid value is 1 mgKOH / g or more, granulation is performed. Sufficient particle size and distribution can be achieved in the process, and when used in toner, sufficient chargeability can be obtained. When the acid value of the polycondensed polyester is 50 mgKOH / g or less, a sufficient molecular weight can be obtained as a toner for polycondensation to obtain image quality strength, and the toner is in a chargeable environment under high humidity. The dependence is small and the image reliability is excellent.
The method for measuring the acid value is not particularly limited, but it is preferable to measure the acid value according to JIS K0070.

When an amorphous polyester resin is used, the glass transition temperature Tg of the amorphous polyester resin is preferably 50 ° C to 80 ° C, more preferably 50 ° C to 65 ° C. When the Tg is 50 ° C. or higher, the cohesive force of the resin itself in a high temperature range is good, so that the hot offset property is excellent at the time of fixing. Further, when Tg is 80 ° C. or lower, sufficient melting is obtained, and the minimum fixing temperature is unlikely to rise.
The glass transition temperature of the resin means a value measured by the method (DSC method) specified in ASTM D3418-82.

Examples of the addition-polymerizable monomer used for producing the addition-polymerizable resin include a cationically polymerizable monomer and a radically polymerizable monomer, and a radically polymerizable monomer is preferable.
Examples of the radically polymerizable monomer include styrene-based monomers, unsaturated carboxylic acids, and (meth) acrylates (note that "(meth) acrylate" means acrylate and methacrylate, and the same applies hereinafter. ), N-vinyl compounds, vinyl esters, vinyl halide compounds, N-substituted unsaturated amides, conjugated dienes, polyfunctional vinyl compounds, polyfunctional (meth) acrylates and the like. .. Among these, N-substituted unsaturated amides, conjugated diene, polyfunctional vinyl compounds, polyfunctional (meth) acrylates, etc. may cause a cross-linking reaction in the produced polymer. it can. These can be used alone or in combination.

Examples of the addition-polymerizable monomer that can be used in the present embodiment include a radical-polymerizable monomer, a cationically polymerizable monomer, and an anionic polymerizable monomer. It is preferable to have.
The radically polymerizable monomer is preferably a compound having an ethylenically unsaturated bond, and has an aromatic ethylenically unsaturated compound (hereinafter, also referred to as “vinyl aromatic”) and an ethylenically unsaturated bond. Carous acids (unsaturated carboxylic acids), derivatives of unsaturated carboxylic acids such as esters and aldehydes, nitriles or amides, N-vinyl compounds, vinyl esters, vinyl halide compounds, N-substituted unsaturated amides, conjugated dienes, poly More preferably, it is a functional vinyl compound or a polyfunctional (meth) acrylate.

Specifically, for example, unsubstituted vinyl aromatics such as styrene and p-vinylpyridine, α-substituted styrene such as α-methylstyrene and α-ethylstyrene, m-methylstyrene, p-methylstyrene, 2, Vinyl aromatics such as aromatic nuclei-substituted styrenes such as 5-dimethylstyrene, p-chlorostyrenes, p-bromostyrenes, dibromostyrenes and the like aromatic nuclei halogen-substituted styrenes, (meth) acrylic acids (Note that "(meth) acrylics" "" Means acrylic and methacryl, and the same shall apply hereinafter.), Unsaturated carboxylic acids such as crotonic acid, maleic acid, fumaric acid, citraconic acid, and itaconic acid, methyl (meth) acrylate, ethyl ( Non-such as meta) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, etc. Saturated carboxylic acid esters, (meth) acrylic aldehyde, (meth) acrylonitrile, unsaturated carboxylic acid derivatives such as (meth) acrylamide, N-vinyl compounds such as N-vinylpyridine and N-vinylpyrrolidone, vinyl formate, Vinyl esters such as vinyl acetate and vinyl propionate, vinyl halide compounds such as vinyl chloride, vinyl bromide and vinylidene chloride, N-methylol acrylamide, N-ethylol acrylamide, N-propanol acrylamide, N-methylol maleamide Acids, N-substituted unsaturated amides such as N-methylol maleiamide, N-methylol maleimide, N-ethylol maleimide, conjugated dienes such as butadiene and isoprene, and many such as divinylbenzene, divinylnaphthalene and divinylcyclohexane. Functional vinyl compounds, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hexamethylene glycol di (Meta) Acrylate, Trimethylol Propane Di (Meta) Acrylate, Trimethylol Propanetri (Meta) Acrylate, Gglycerol Di (Meta) Acrylate, Gglycerol Tri (Meta) Acrylate, Pentaerythritol Di (Meta) Acrylate, Pentaerythri Thortri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Examples thereof include polyfunctional acrylates such as dipentaerythritol hexa (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, sorbitol penta (meth) acrylate, and sorbitol hexa (meth) acrylate. Further, sulfonic acids and phosphonic acids having an ethylenically unsaturated bond and derivatives thereof can also be used. Among these, N-substituted unsaturated amides, conjugated diene, polyfunctional vinyl compounds, polyfunctional acrylates and the like can also cause a cross-linking reaction in the produced polymer. Further, these addition-polymerizable monomers may be used alone or in combination of two or more.

The weight average molecular weight (Mw) of the crystalline resin in the melt mixture is larger than the weight average molecular weight (Mw) of the amorphous resin in the melt mixture from the viewpoint of fixability and transferability in the obtained toner. A small value is preferable.
Further, when two or more kinds of the amorphous resin are used, that is, when the amorphous resin has two or more peaks in the molecular weight distribution of the amorphous resin in the melt mixture, the crystalline resin in the melt mixture is used. The weight average molecular weight is the weight average molecular weight of at least one peak and the weight average molecular weight of the other one peak in the molecular weight distribution of the amorphous resin in the melt mixture from the viewpoint of fixability and transferability in the obtained toner. It is more preferable that the value is between.

Further, the weight average molecular weight (Mw) of at least one peak in the molecular weight distribution of the amorphous resin in the molten mixture is 5,000 or more and 1,000, from the viewpoint of fixability and transferability in the obtained toner. It is preferably 000 or less, more preferably 7,000 or more and 500,000 or less, and particularly preferably 8,000 or more and 200,000 or less.
Further, the difference between the weight average molecular weight of the crystalline resin in the melt mixture and the weight average molecular weight of the peak of the largest molecular weight in the molecular weight distribution of the amorphous resin in the melt mixture is the fixability in the obtained toner. From the viewpoint of transferability, it is preferably 1,000 or more and 500,000 or less, more preferably 1,000 or more and 200,000 or less, and particularly preferably 5,000 or more and 100,000 or less. ..

_{The content W Max of the} amorphous resin (also referred to as "amorphous resin Max") showing the highest molecular weight peak in the molecular weight distribution of the amorphous resin in the molten mixture, and the said in the molten mixture. the value of the ratio of the content _{M C} of the crystalline resin ^_(M Max / _M ^C), from the viewpoint of the fixing property and transfer property in the resulting toner is preferably 10 or more and 100 or less, at 20 to 80. It is more preferable that there is, and it is particularly preferable that it is 30 or more and 70 or less.
The acid value of the amorphous resin Max is preferably higher than the acid value of the crystalline resin in the molten mixture from the viewpoint of fixability and transferability in the obtained toner.
Further, in the molten mixture, the value of (weight average molecular weight of the amorphous resin Max) / (acid value of the amorphous resin Max (mgKOH / g)) is the fixability and transferability in the obtained toner. From the above viewpoint, it is preferably 2,000 or more and 15,000 or less, more preferably 4,000 or more and 10,000 or less, and particularly preferably 6,000 or more and 8,000 or less.
Further, in the molten mixture, the value of (weight average molecular weight of the crystalline resin) / (acid value of the crystalline resin (mgKOH / g)) is determined from the viewpoint of fixability and transferability in the obtained toner. It is preferably 1,000 or more and 10,000 or less, more preferably 1,500 or more and 7,000 or less, and particularly preferably 2,000 or more and 5,000 or less.

(Emulsification process)
The method for producing a resin particle dispersion liquid according to the present embodiment includes an emulsification step of adding an aqueous medium to emulsify the molten mixture while applying a shearing force.
The emulsification dispersion in the emulsification step is preferably carried out by phase inversion emulsification. That is, in the emulsification step, it is preferable to continuously or sequentially add an aqueous medium to the melt mixture to emulsify and disperse, and it is possible to sequentially add an aqueous medium to the melt mixture two or more times to emulsify and disperse. More preferably, an aqueous medium is sequentially added to the molten mixture three times or more and emulsified and dispersed.
The emulsification dispersion in the emulsification step is performed while applying a shearing force to the molten mixture. Further, it is preferable to use an extruder or a kneader in the emulsification step. For example, it is preferable that a shearing force is applied to the molten mixture by a screw of an extruder, a blade of a kneader, or the like.

Examples of the aqueous medium used in the present embodiment include water such as distilled water and ion-exchanged water, and alcohols such as ethanol and methanol. Among these, ethanol and water are preferable, and water such as distilled water and ion-exchanged water is particularly preferable. These may be used alone or in combination of two or more.
Further, the aqueous medium may contain a water-miscible organic solvent, but it is preferable not to contain it in the emulsification step.
The amount of the aqueous medium used in the emulsification step is not particularly limited, but may be appropriately selected depending on the solid content concentration of the obtained resin particle dispersion liquid.
The solid content concentration of the obtained resin particle dispersion may be appropriately selected as necessary, but is preferably 1% by mass or more and 60% by mass or less, and more preferably 5% by mass or more and 50% by mass or less. It is particularly preferably 10% by mass or more and 50% by mass or less.

The emulsification temperature in the emulsification step is not particularly limited, but is preferably 50 ° C. to 150 ° C., more preferably 50 ° C. to 100 ° C. from the viewpoint of emulsification dispersibility in the emulsification step.
The emulsification temperature in the emulsification step is preferably a temperature equal to or higher than the glass transition temperature (Tg) of the amorphous resin, and more preferably a temperature of Tg + 5 ° C. or higher of the amorphous resin.

The emulsifying means used in the emulsification step is not particularly limited, and a known disperser or emulsifying device may be used. For example, a kneader, a homogenizer, a homomixer, a pressurized kneader, an extruder, a media disperser, a uniaxial or Examples include a twin-screw extruder.
Among them, an extruder and a kneader are preferably mentioned.
The emulsifying device used in the emulsification step is not particularly limited to a batch type or a continuous type, but a twin-screw extruder as illustrated in FIG. 1 can be preferably mentioned.
FIG. 1 is a schematic configuration diagram showing an example of a manufacturing apparatus preferably used in the method for manufacturing a resin particle dispersion liquid according to the present embodiment.
The twin-screw extruder 210 shown in FIG. 1 is provided with a twin-screw screw (not shown) inside the cylinder 212, and the cylinder 212 includes a raw material input port 214, a base aqueous solution input port 216, and a surfactant input port 218. It has water inlets 220, 221 and 222, and outlets 224. Further, a pH measuring device (not shown) for monitoring pH, and a cooling facility (not shown) may be provided after the discharge port. A supply line 226 for supplying raw materials is connected to each inlet, and each supply line is provided with a pump 228 whose supply amount can be adjusted as needed. A resin feeder 230 is connected to the raw material input port 214 by a supply line 226. A base aqueous solution input port 216 is provided on the side wall of the raw material input port 214, and a base aqueous solution tank 232 is connected to the base aqueous solution input port 216 by a supply line 226. A surfactant aqueous solution tank 234 is connected to the surfactant inlet 218 by a supply line 226, and the surfactant aqueous solution tank 234 is provided with a temperature control device 236 such as a constant temperature bath. A pure water tank 238 is connected to each of the water inlets 220, 221 and 222 by a supply line 226, and the pure water tank 238 is provided with a heater 240.

The positions of the surfactant inlet and the water inlet are not particularly limited, and the configuration as shown in FIG. 1 can be adopted, and as shown in FIG. 1, the postponed aqueous solution inlet 216 and the surfactant before adding water are added. The agent inlet is arranged. The cylinder 212 in the twin-screw extruder 210 shown in FIG. 1 has a section called a resin supply barrel 242, and for example, the structure of the twin-screw screw can be changed or the temperature control can be changed for each barrel. can do. Water inlets 220, 221 and 222 can be provided in each barrel of the cylinder portion 244 other than the resin supply barrel 242, if desired. In FIG. 1, each barrel in the cylinder 212 is a section divided by a dotted line. Further, the twin-screw extruder 210 includes a temperature control device (not shown). The screw (not shown) provided inside the cylinder 212 shown in FIG. 1 is not particularly limited, but is composed of a kneading disc element and a screw element, and is configured by combining a plurality of types of kneading disc elements and screw elements. Is preferable.

The method for producing the resin particle dispersion liquid according to the present embodiment may include other steps other than the melting step and the emulsifying step.
The other steps are not particularly limited, and a known step can be performed as needed, and examples thereof include a step of cooling the obtained resin particle dispersion liquid.

(Physical characteristics of resin particles in the resin particle dispersion)
The average particle size (volume average particle size) of the resin particles in the obtained resin particle dispersion is preferably in the range of 60 nm or more and 300 nm or less, and more preferably in the range of 120 nm or more and 250 nm or less. Within the above range, the cohesiveness of the resin particles is sufficient, and the particle size distribution of the toner can be narrowed.
The volume average particle size of the resin particles is divided into particle size ranges (channels) using the particle size distribution obtained by measurement with a laser diffraction type particle size distribution measuring device (for example, LA-700 manufactured by Horiba Seisakusho Co., Ltd.). On the other hand, the cumulative distribution of the volume is subtracted from the small particle size side, and the particle size that is cumulatively 50% of all particles is measured as the volume average particle size D50v.

The content of sulfur atoms in the resin particles in the resin particle dispersion is preferably 0.01% by mass or more and 1.5% by mass or less from the viewpoint of fixability and transferability of the obtained toner. It is more preferably 03% by mass or more and 1% by mass or less, and particularly preferably 0.06% by mass or more and 0.6% by mass or less.
The sulfur atom in the resin particles in the resin particle dispersion may have any valence.

The content of alkali metal atoms in the resin particles in the resin particle dispersion is more preferably 0.05% by mass or more and 2% by mass or less from the viewpoint of fixability and transferability of the obtained toner. It is more preferably 1% by mass or more and 1.5% by mass or less, and particularly preferably 0.15% by mass or more and 1% by mass or less.
The alkali metal atom in the resin particles in the resin particle dispersion may have any valence.
Further, 50% by mass or more of the content of the alkali metal atom is preferably a sodium atom, 80% by mass or more is more preferably a sodium atom, and 90% by mass or more is a sodium atom. It is particularly preferable to have.

Here, examples of the source of sulfur atoms include additives (surfactants and the like) containing sulfur atoms.
Further, as a source of the alkali metal atom, an additive containing a sodium salt (surfactant, basic compound, etc.) can be mentioned.
Examples of the surfactant include a surfactant used for the purpose of dispersing various particles in a dispersion liquid when toner particles are produced by the aggregation and coalescence method. Specific examples of the surfactant include anionic surfactants such as sulfate ester-based, sulfonic acid-based, polyacrylic acid-based, phosphoric acid ester-based, and soap-based sodium salts.
In addition, as an additive that is a source of alkali metal atoms, sodium chloride (NaCl) and the like can also be mentioned.

Specifically, for example, the source of the sulfur atom is derived from sulfate (metal sulfate, dodecylbenzene sulfonic acid metal salt, metal sulfide, etc.) and sulfonate (dodecylbenzene sulfonic acid metal salt, dodecyl). Sulfur atoms derived from metal sulfates are preferred.
Specifically, the source of the alkali metal atom is preferably a sodium atom derived from a sodium salt (sodium sulfate, sodium dodecylbenzene sulfonate, sodium hydroxide, sodium chloride, sodium nitrate, sodium dialkyl sulfosuccinate, etc.). Be done.

The content of sulfur atoms and the content of alkali metal atoms in the resin particles in the resin particle dispersion liquid shall be measured by the following methods.
50 g of the resin particle dispersion is sealed in a dialysis membrane (Dialesis membrane, size 36, manufactured by Wako Pure Chemical Industries, Ltd.) and immersed in 10 L of pure water for 5 days with stirring (pure water is replaced every day). Remove impurities in the dispersion. Then, the resin particle dispersion liquid subjected to the dialysis treatment was dried using a freeze dryer. Using a fluorescent X-ray analyzer (scanning fluorescent X-ray analyzer, ZSX PrimusII, manufactured by Rigaku Co., Ltd.), the net strength of the sulfur atomic weight and alkali metal atomic weight contained in the dried resin particles was measured. , Calculate the atomic weight of sulfur and the atomic weight of alkali metal in the resin particles from the calibration curve prepared in advance. As a sample pretreatment, 0.1 g to 0.2 g of dried resin particles are disc-molded by pressure molding, and the measurement conditions are qualitative quantitative measurement, tube voltage 40 kV, tube current 70 mA, measurement time 15 minutes. Measure.

<Resin particle dispersion>
The resin particle dispersion liquid according to the present embodiment contains resin particles containing an amorphous resin, a crystalline resin, a surfactant, and a basic compound, and the content of the surfactant is the total mass of the resin particles. The content of the basic compound in the resin particle dispersion is 0.05 mol or more and 0.2 by mass with respect to 1 kg of the resin in the resin particle dispersion. The molar content of the sulfur atom in the resin particles is 0.03% by mass or more and 1% by mass or less, and the content of the alkali metal atom in the resin particles is 0.1% by mass or more and 1.5% by mass or less. It is less than or equal to mass%.
Further, the resin particle dispersion liquid according to the present embodiment is preferably a resin particle dispersion liquid produced by the method for producing the resin particle dispersion liquid according to the present embodiment.
Further, the resin particle dispersion liquid according to the present embodiment is suitably used as a resin particle dispersion liquid for a binder resin of a toner for static charge image development.

The preferred embodiment of the resin particle dispersion liquid according to the present embodiment is the same as the preferred embodiment of the resin particle dispersion liquid produced by the method for producing the resin particle dispersion liquid according to the present embodiment described above, except as described later.
The same applies to the methods for measuring various physical property values.

The content of the surfactant in the resin particle dispersion is 1% by mass or more and 5% by mass or less with respect to the total mass of the resin particles, and 1% by mass from the viewpoint of fixability and transferability in the obtained toner. % Or more and 4% by mass or less, more preferably 1.5% by mass or more and 3.5% by mass or less, and particularly preferably 2.5% by mass or more and 3.5% by mass or less. Within the above range, the emulsion dispersibility is excellent, and the toner fixability and transferability are excellent.

The content of the basic compound in the resin particle dispersion is 0.05 mol or more and 0.2 mol or less with respect to 1 kg of the resin in the resin particle dispersion, and the fixability and transferability of the obtained toner are improved. From the viewpoint, it is preferably 0.05 mol or more and 0.18 mol or less, more preferably 0.08 mol or more and 0.15 mol or less, and more preferably 0.08 mol or more and 0.12 mol or less. Especially preferable. Within the above range, the emulsion dispersibility is excellent, and the toner fixability and transferability are excellent.
The content of the basic compound includes not only the content of the basic compound in the resin particles but also the content of the basic compound in the dispersion medium such as an aqueous medium. Is the total content of.

The content of sulfur atoms in the resin particles in the resin particle dispersion is 0.03% by mass or more and 1% by mass or less, and from the viewpoint of the fixability and transferability of the obtained toner, 0.06% by mass or more and 0. It is preferably 6.6% by mass or less.
The sulfur atom in the resin particles in the resin particle dispersion may have any valence.

The content of alkali metal atoms in the resin particles in the resin particle dispersion is 0.1% by mass or more and 1.5% by mass or less, and from the viewpoint of the fixability and transferability of the obtained toner, 0.15% by mass. It is preferably% or more and 1% by mass or less.
The alkali metal atom in the resin particle dispersion may have any valence.
Further, 50% by mass or more of the content of alkali metal atoms in the resin particle dispersion is preferably sodium atoms, and 80% by mass or more is more preferably sodium atoms, 90% by mass. The above is particularly preferably a sodium atom.

<Static charge image developing toner and its manufacturing method>
The static charge image developing toner according to the present embodiment is a toner using at least the resin particles dispersed in the resin particle dispersion liquid obtained by the method for producing the resin particle dispersion liquid according to the present embodiment as a binder resin. ..
The method for producing a toner for static charge image development according to the present embodiment includes an agglomeration step of forming agglomerated particles containing resin particles and a fusion step of forming toner particles by fusing the agglomerated particles. The resin particles include the resin particles contained in the resin particle dispersion liquid produced by the method for producing the resin particle dispersion liquid according to the present embodiment.
The toner according to the present embodiment is composed of toner matrix particles (also referred to as “toner particles”) and, if necessary, an external additive.

(Bundling resin)
The binder resin in the toner for developing an electrostatic charge image according to the present embodiment contains at least a resin derived from the resin particle dispersion liquid obtained by the method for producing the resin particle dispersion liquid according to the present embodiment.
The toner for static charge image development according to the present embodiment may contain a resin other than the resin derived from the resin particle dispersion liquid obtained by the method for producing the resin particle dispersion liquid according to the present embodiment as the binder resin. However, it is preferably less than 60% by mass, more preferably 20% by mass or less, still more preferably 10% by mass or less, and not contained in the total weight of the binder resin contained in the toner. Is particularly preferable. In the above aspect, the fixing characteristics are more excellent.
Further, as the toner for static charge image development according to the present embodiment, one kind of resin derived from the resin particle dispersion liquid obtained by the method for producing the resin particle dispersion liquid according to the present embodiment is used alone as the binder resin. However, two or more types may be used in combination.
The resin other than the resin derived from the resin particle dispersion obtained by the method for producing the resin particle dispersion according to the present embodiment is not particularly limited, and a known resin used for toner is used.

The content of the binder resin is preferably 40% by mass or more and 95% by mass or less, more preferably 50% by mass or more and 90% by mass or less, and further preferably 60% by mass or more and 85% by mass or less with respect to the entire toner particles.

-Colorant-
Examples of colorants include carbon black, chrome yellow, Hansa yellow, benzine yellow, slene yellow, quinoline yellow, pigment yellow, permanent orange GTR, pyrazolone orange, vulcan orange, watch young red, permanent red, brilliant carmine 3B, and brilliant. Carmin 6B, Dupont Oil Red, Pyrazolon Red, Resole Red, Rhodamin B Lake, Lake Red C, Pigment Red, Rose Bengal, Aniline Blue, Ultra Marine Blue, Calco Oil Blue, Methylene Blue Chloride, Phthalocyanine Blue, Pigment Blue, Phthalocyanine Green, Various pigments such as malachite green oxalate, or aclysine, xanthene, azo, benzoquinone, azine, anthraquinone, thioindico, dioxazine, thiazine, azomethine, indico, phthalocyanine, aniline black Examples thereof include various dyes such as system, polymethine type, triphenylmethane type, diphenylmethane type and thiazole type.
The colorant may be used alone or in combination of two or more.

As the colorant, a surface-treated colorant may be used if necessary, or may be used in combination with a dispersant. Further, a plurality of kinds of colorants may be used in combination.

The content of the colorant is, for example, preferably 1% by mass or more and 30% by mass or less, and more preferably 3% by mass or more and 15% by mass or less with respect to the entire toner particles.

-Release agent-
Examples of the release agent include hydrocarbon waxes; natural waxes such as carnauba wax, rice wax and candelilla wax; synthetic or mineral / petroleum waxes such as montan wax; ester waxes such as fatty acid esters and montanic acid esters. ; And so on. The release agent is not limited to this.

The melting temperature of the release agent is preferably 50 ° C. or higher and 110 ° C. or lower, and more preferably 60 ° C. or higher and 100 ° C. or lower.
The melting temperature is determined from the DSC curve obtained by differential scanning calorimetry (DSC) by the "melting peak temperature" described in the method for determining the melting temperature in JIS K 7121-1987 "Method for measuring transition temperature of plastics". ..

The content of the release agent is, for example, preferably 1% by mass or more and 20% by mass or less, and more preferably 5% by mass or more and 15% by mass or less with respect to the entire toner particles.

-Other additives-
Examples of other additives include well-known additives such as magnetic materials, charge control agents, and inorganic powders. These additives are contained in the toner particles as an internal additive.

-Characteristics of toner particles, etc.-
The toner particles may be toner particles having a single layer structure, or are toner particles having a so-called core-shell structure composed of a core portion (core particles) and a coating layer (shell layer) covering the core portion. You may.
Here, the toner particles having a core-shell structure include, for example, a core portion composed of a binder resin and, if necessary, other additives such as a colorant and a mold release agent, and a binder resin. It is preferably composed of a composed coating layer.

The volume average particle size (D50v) of the toner particles is preferably 2 μm or more and 10 μm or less, and more preferably 4 μm or more and 8 μm or less.

The various average particle sizes and various particle size distribution indexes of the toner particles were measured using Coulter Multisizer II (manufactured by Beckman Coulter), and the electrolytic solution was measured using ISOTON-II (manufactured by Beckman Coulter). Toner.
At the time of measurement, 0.5 mg or more and 50 mg or less of the measurement sample is added to 2 ml of a 5% aqueous solution of a surfactant (preferably sodium alkylbenzene sulfonate) as a dispersant. This is added to 100 ml or more and 150 ml or less of the electrolytic solution.
The electrolytic solution in which the sample is suspended is dispersed for 1 minute with an ultrasonic disperser, and the particle size distribution of particles having a particle size in the range of 2 μm or more and 60 μm or less is obtained by using a Coulter Multisizer II with an aperture of 100 μm. Measure. The number of particles to be sampled is 50,000.
Cumulative distribution of volume and number is drawn from the small diameter side for each particle size range (channel) divided based on the measured particle size distribution, and the cumulative 16% particle size is volume particle size D16v, number particle size The particle size having D16p and a cumulative 50% is defined as the volume average particle size D50v and the cumulative number average particle size D50p, and the particle size having a cumulative number of 84% is defined as the volume particle size D84v and the number particle size D84p.
Using these, the volume particle size distribution index (GSDv) is calculated as (D84v / D16v) ^1/2 , and the number particle size distribution index (GSDp) is calculated as ^{(D84p / D16p) 1/2.}

The average circularity of the toner particles is preferably 0.94 or more and 1.00 or less, and more preferably 0.95 or more and 0.98 or less.

The average circularity of the toner particles is obtained by (circumferential peripheral length) / (circumferential length) [(circumferential length of a circle having the same projected area as the particle image) / (peripheral length of the particle projected image)]. Specifically, it is a value measured by the following method.
First, a flow-type particle image analyzer (Cysmex) that captures a particle image as a still image by sucking and collecting toner particles to be measured, forming a flat flow, and instantly causing strobe light emission to analyze the particle image. Obtained by FPIA-3000) manufactured by Co., Ltd. Then, the number of samples for obtaining the average circularity is set to 3,500.
When the toner has an external additive, the toner (developer) to be measured is dispersed in water containing a surfactant, and then ultrasonic treatment is performed to obtain toner particles from which the external additive has been removed. ..

(External agent)
Examples of the external additive include inorganic particles. As the inorganic particles, SiO ₂ , TiO ₂ , Al ₂ O ₃ , CuO, ZnO, SnO ₂ , CeO ₂ , Fe ₂ O ₃ , MgO, BaO, CaO, K ₂ O, Na ₂ O, ZrO ₂ , CaO. _{SiO 2, K 2 O · (} TiO 2) n, Al 2 O 3 · 2SiO 2, CaCO 3, MgCO 3, BaSO 4, MgSO 4 , and the like.

The surface of the inorganic particles as an external additive should be hydrophobized. The hydrophobizing treatment is performed, for example, by immersing inorganic particles in a hydrophobizing agent. The hydrophobizing agent is not particularly limited, and examples thereof include a silane-based coupling agent, a silicone oil, a titanate-based coupling agent, and an aluminum-based coupling agent. These may be used alone or in combination of two or more.
The amount of the hydrophobizing agent is preferably 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the inorganic particles.

Examples of the external additive include resin particles (resin particles such as polystyrene, polymethylmethacrylate (PMMA), and melamine resin), cleaning activators (for example, metal salts of higher fatty acids typified by zinc stearate, fluoropolymers). Particles) and the like.

The amount of the external additive added is preferably, for example, 0.01% by mass or more and 5% by mass or less, and more preferably 0.01% by mass or more and 2.0% by mass or less with respect to the toner particles.

(Sulfur atom content and alkali metal atom content in toner)
The content of sulfur atoms in the toner is preferably 0.06% by mass or more and 0.15% by mass or less, and 0.07% by mass or more and 0. 13% by mass or less is more preferable, and 0.08% by mass or more and 0.11% by mass or less is particularly preferable.

Here, examples of the source of sulfur atoms include additives containing sulfur atoms (surfactants, flocculants, etc.).
Examples of the surfactant include the above-mentioned surfactant in the method for producing a resin particle dispersion liquid.
Examples of the aggregating agent include an aggregating agent used for the purpose of aggregating various particles when the toner particles are produced by the aggregating and coalescing method. Specifically, examples of the flocculant include aluminum sulfate, magnesium sulfate, potassium sulfate, sodium sulfate, calcium sulfate, zinc sulfate and the like.
The content of sulfur atoms can be adjusted by adjusting the amount of these additives. The content of sulfur atoms can also be adjusted by adjusting the amount of chelating agent for removing the flocculant.

The content of alkali metal atoms in the toner is preferably 0.05% by mass or more and 0.25% by mass or less, and 0.10% by mass or more and 0, from the viewpoint of charge stability and fixed image strength in a high temperature and high humidity environment. .20% by mass or less is more preferable, and 0.12% by mass or more and 0.15% by mass or less is particularly preferable.

Here, examples of the source of the alkali metal atom include additives containing sodium salts (surfactants, basic compounds, flocculants, etc.).
Examples of the surfactant and the basic compound include the above-mentioned surfactant and the basic compound in the method for producing the resin particle dispersion liquid.
Examples of the aggregating agent include an aggregating agent used for the purpose of aggregating various particles when the toner particles are produced by the aggregating and coalescing method. Specifically, examples of the flocculant include sodium sulfate and the like.
In addition, as an additive that is a source of alkali metal atoms, sodium chloride (NaCl) and the like can also be mentioned.
The content of alkali metal atoms can be adjusted by adjusting the amount of these additives. The content of the alkali metal atom can also be adjusted by the amount of the chelating agent for removing the flocculant.

The content of sulfur atoms and the content of alkali metal atoms in the toner shall be measured by the following methods.
Using a fluorescent X-ray analyzer (scanning fluorescent X-ray analyzer, ZSX PrimusII, manufactured by Rigaku Co., Ltd.), the toner contains sulfur atoms and alkali metal atoms. The strength is measured, and the content of sulfur atoms and the content of alkali metal atoms in the toner are calculated from the calibration curve prepared in advance. As a sample pretreatment, 0.1 g to 0.2 g of dried toner is disk-molded by pressure molding, and the measurement conditions are qualitative quantitative measurement, tube voltage 40 kV, tube current 70 mA, and measurement time 15 minutes. To do.

(Toner manufacturing method)
Next, a method for producing toner according to this embodiment will be described.
The method for producing a toner according to the present embodiment includes an agglomeration step of forming agglomerated particles containing resin particles and a fusion step of forming toner particles by fusing the agglomerated particles, and the resin particles are present. The resin particles contained in the resin particle dispersion liquid produced by the method for producing the resin particle dispersion liquid according to the embodiment are included.
The toner according to the present embodiment can be obtained by externally adding an external additive to the toner particles after producing the toner particles.

As described above, the toner particles are obtained by the aggregation and coalescence method.
Specifically, for example, a step of preparing a resin particle dispersion liquid in which resin particles to be a binder resin are dispersed (resin particle dispersion liquid preparation step) and a step of preparing other particles in the resin particle dispersion liquid (if necessary). A step of aggregating resin particles (other particles if necessary) to form agglomerated particles (aggregated particle forming step) and agglomerated particles in which the agglomerated particles are dispersed. The dispersion liquid is heated to fuse and coalesce the aggregated particles to form toner particles (fusion and coalescence step), and then the toner particles are produced.
As the binder resin, it is preferable to use a polyester resin having an acid value of 1 mgKOH / g or more and 50 mgKOH / g or less.

The details of each step will be described below.
In the following description, a method of obtaining toner particles containing a colorant and a mold release agent will be described, but the colorant and the mold release agent are used as needed. Of course, other additives other than colorants and mold release agents may be used.

-Resin particle dispersion liquid preparation process-
The resin particles used in the method for producing toner in the present embodiment include resin particles contained in the resin particle dispersion liquid produced by the method for producing the resin particle dispersion liquid according to the present embodiment.
As the resin particle dispersion liquid, at least the resin particle dispersion liquid produced by the method for producing the resin particle dispersion liquid according to the present embodiment is used.
Further, together with the resin particle dispersion liquid, for example, a colorant dispersion liquid in which a colorant is dispersed and a mold release agent dispersion liquid in which a mold release agent is dispersed are prepared.
The colorant dispersion and the release agent dispersion are prepared by a known method.

[Method for producing colorant dispersion]
The colorant dispersion liquid is formed by at least dispersing the colorant.
The colorant is dispersed by a known method, and for example, a media type disperser such as a rotary shear type homogenizer, a ball mill, a sand mill, or an attritor, a high pressure opposed collision type disperser, or the like is preferably used. Further, as the colorant, a polar ionic surfactant may be used and dispersed in an aqueous solvent using a homogenizer as described above to prepare a colorant dispersion liquid. The colorant may be used alone or in combination of two or more. The volume average particle size of the colorant (hereinafter, may be simply referred to as the average particle size) is preferably 1 μm or less, more preferably 0.5 μm or less, and 0.01 μm or more and 0.5 μm. The following is particularly preferable.
Further, as a dispersant added to further stabilize the dispersion stability of the colorant in an aqueous medium and lower the energy of the colorant in the toner, rosin, a rosin derivative, a coupling agent, and a polymer dispersion are used. Agents and the like can be mentioned.

[Method for producing release agent dispersion]
The release agent dispersion liquid is formed by dispersing at least the release agent.
The release agent is dispersed by a known method, and for example, a media type disperser such as a rotary shear type homogenizer, a ball mill, a sand mill, or an attritor, a high pressure opposed collision type disperser, or the like is preferably used. Further, the release agent may be an ionic surfactant having polarity and dispersed in an aqueous solvent using a homogenizer as described above to prepare a release agent particle dispersion liquid. In the present embodiment, the release agent may be used alone or in combination of two or more. The average particle size of the release agent particles is preferably 1 μm or less, more preferably 0.01 μm or more and 1 μm or less.

-Agglomerated particle formation process-
Next, the colorant dispersion and the release agent dispersion are mixed together with the resin particle dispersion.
Then, in the mixed dispersion liquid, the resin particles, the colorant, and the release agent are hetero-aggregated, and the aggregated particles containing the resin particles, the colorant, and the release agent having a diameter close to the diameter of the target toner particles are formed. Form.

Specifically, for example, a flocculant is added to the mixed dispersion, the pH of the mixed dispersion is adjusted to acidic (for example, the pH is 2 or more and 5 or less), and a dispersion stabilizer is added as necessary. The particles are heated to a temperature of the glass transition temperature of the resin particles (specifically, for example, the glass transition temperature of the resin particles is -30 ° C or higher and the glass transition temperature is -10 ° C or lower), and the particles dispersed in the mixed dispersion are aggregated. , Form agglomerated particles.
In the agglomerated particle forming step, for example, the mixed dispersion is stirred with a rotary shear type homogenizer, the aggregating agent is added at room temperature (for example, 25 ° C.), and the pH of the mixed dispersion is acidic (for example, pH is 2 or more and 5 or less). ), And if necessary, a dispersion stabilizer may be added, and then the heating may be carried out.

Examples of the flocculant include a surfactant used as a dispersant added to the mixed dispersion, a surfactant having the opposite polarity, an inorganic metal salt, and a divalent or higher metal complex. In particular, when a metal complex is used as the flocculant, the amount of the surfactant used is reduced and the charging characteristics are improved.
If necessary, an additive that forms a complex or a similar bond with the metal ion of the flocculant may be used. As this additive, a chelating agent is preferably used.

Examples of the inorganic metal salt include metal salts such as calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride and aluminum sulfate, and inorganics such as polyaluminum chloride, polyaluminum hydroxide and calcium polysulfide. Examples include metal salt polymers.
As the chelating agent, a water-soluble chelating agent may be used. Examples of the chelating agent include oxycarboxylic acids such as tartrate acid, citric acid and gluconic acid, iminodic acid (IDA), nitrilotriacetic acid (NTA) and ethylenediaminetetraacetic acid (EDTA).
The amount of the chelating agent added is, for example, preferably 0.01 parts by mass or more and 5.0 parts by mass or less, and more preferably 0.1 parts by mass or more and less than 3.0 parts by mass with respect to 100 parts by mass of the resin particles.

-Fusion / unification process-
Next, the agglomerated particle dispersion liquid in which the agglomerated particles are dispersed is heated to, for example, a glass transition temperature of the resin particles or higher (for example, a temperature 10 ° C. to 30 ° C. higher than the glass transition temperature of the resin particles) to agglomerate. The particles are fused and united to form toner particles.

Toner particles are obtained through the above steps.
After obtaining the agglomerated particle dispersion liquid in which the agglomerated particles are dispersed, the agglomerated particle dispersion liquid and the resin particle dispersion liquid in which the resin particles are dispersed are further mixed, and further resin particles are added to the surface of the agglomerated particles. The step of aggregating so as to adhere to form the second agglomerated particles and the second agglomerated particle dispersion liquid in which the second agglomerated particles are dispersed are heated to fuse and unite the second agglomerated particles. , Toner particles may be produced through a step of forming toner particles having a core / shell structure.

Here, after the fusion / coalescence step is completed, the toner particles formed in the solution are subjected to a known washing step, solid-liquid separation step, and drying step to obtain toner particles in a dried state.
In the cleaning step, it is preferable to sufficiently perform replacement cleaning with ion-exchanged water from the viewpoint of chargeability. The solid-liquid separation step is not particularly limited, but suction filtration, pressure filtration, or the like may be performed from the viewpoint of productivity. The drying step is also not particularly limited, but from the viewpoint of productivity, freeze-drying, air-flow drying, fluid-drying, vibration-type fluid-drying, and the like may be performed.

Then, the toner according to the present embodiment is produced, for example, by adding an external additive to the obtained dry toner particles and mixing them. The mixing may be carried out by, for example, a V blender, a Henschel mixer, a Ladyge mixer or the like. Further, if necessary, coarse particles of toner may be removed by using a vibration sieving machine, a wind sieving machine, or the like.

<Static charge image developer>
The electrostatic charge image developer according to the present embodiment contains at least the toner produced by the method for producing the toner according to the present embodiment.
The electrostatic charge image developer according to the present embodiment may be a one-component developer containing only the toner according to the present embodiment, or a two-component developer mixed with the toner and a carrier.

The carrier is not particularly limited, and examples thereof include known carriers. As the carrier, for example, a coating carrier in which the surface of a core material made of magnetic powder is coated with a coating resin; a magnetic powder dispersion type carrier in which magnetic powder is dispersed and blended in a matrix resin; a porous magnetic powder is impregnated with resin. Resin-impregnated carrier; etc.
The magnetic powder dispersion type carrier and the resin impregnated type carrier may be carriers in which the constituent particles of the carrier are used as a core material and coated with a coating resin.

Examples of the magnetic powder include magnetic metals such as iron, nickel and cobalt, and magnetic oxides such as ferrite and magnetite.

Examples of the coating resin and matrix resin include polyethylene, polypropylene, polystyrene, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl ether, polyvinyl ketone, vinyl chloride-vinyl acetate copolymer, and styrene-acrylic acid ester. Examples thereof include a copolymer, a straight silicone resin containing an organosiloxane bond or a modified product thereof, a fluororesin, a polyester, a polypropylene, a phenol resin, an epoxy resin and the like.
The coating resin and the matrix resin may contain other additives such as conductive particles.
Examples of the conductive particles include metals such as gold, silver and copper, and particles such as carbon black, titanium oxide, zinc oxide, tin oxide, barium sulfate, aluminum borate and potassium titanate.

Here, in order to coat the surface of the core material with the coating resin, a method of coating with a coating resin and, if necessary, a coating layer forming solution in which various additives are dissolved in an appropriate solvent and the like can be mentioned. The solvent is not particularly limited, and may be selected in consideration of the coating resin to be used, coating suitability, and the like.
Specific resin coating methods include a dipping method in which the core material is immersed in a coating layer forming solution, a spray method in which the coating layer forming solution is sprayed on the core material surface, and a state in which the core material is suspended by flowing air. Examples thereof include a fluidized bed method in which a coating layer forming solution is sprayed, a kneader coater method in which a carrier core material and a coating layer forming solution are mixed in a kneader coater, and a solvent is removed.

The mixing ratio (mass ratio) of the toner and the carrier in the two-component developer is preferably toner: carrier = 1: 100 to 30: 100, and more preferably 3: 100 to 20: 100.

<Image forming device / Image forming method>
The image forming apparatus / image forming method according to the present embodiment will be described.
The image forming apparatus according to the present embodiment includes an image holder, a charging means for charging the surface of the image holder, a static charge image forming means for forming an electrostatic charge image on the surface of the charged image holder, and an electrostatic charge. A developing means that accommodates an image developer and develops an electrostatic charge image formed on the surface of the image holder as a toner image by the static charge image developer, and a recording medium that records the toner image formed on the surface of the image holder. It is provided with a transfer means for transferring to the surface of the recording medium and a fixing means for fixing the toner image transferred to the surface of the recording medium. Then, as the electrostatic charge image developer, the electrostatic charge image developer according to the present embodiment is applied.

In the image forming apparatus according to the present embodiment, a charging step of charging the surface of the image holder, a static charge image forming step of forming an electrostatic charge image on the surface of the charged image holder, and an electrostatic charge according to the present embodiment. A development step of developing an electrostatic charge image formed on the surface of an image holder as a toner image with an image developer, and a transfer step of transferring a toner image formed on the surface of the image holder to the surface of a recording medium. An image forming method (image forming method according to the present embodiment) having a fixing step of fixing a toner image transferred to the surface of a recording medium is carried out.

The image forming apparatus according to the present embodiment is a direct transfer type apparatus that directly transfers the toner image formed on the surface of the image holder to the recording medium; the toner image formed on the surface of the image holder is transferred to the intermediate transfer body. An intermediate transfer type device that first transfers the toner image to the surface and then secondarily transfers the toner image transferred to the surface of the intermediate transfer body to the surface of the recording medium; after transferring the toner image, cleans the surface of the image holder before charging. A device provided with a cleaning means; a well-known image forming device such as a device provided with a static elimination means for irradiating the surface of an image holder with static elimination light after transfer of a toner image and before charging is applied.
In the case of an intermediate transfer type apparatus, the transfer means is, for example, an intermediate transfer body in which a toner image is transferred to the surface and a primary transfer in which a toner image formed on the surface of an image holder is primarily transferred to the surface of the intermediate transfer body. A configuration comprising means and secondary transfer means for secondary transfer of the toner image transferred to the surface of the intermediate transfer body to the surface of the recording medium is applied.

In the image forming apparatus according to the present embodiment, for example, the portion including the developing means may have a cartridge structure (process cartridge) that is attached to and detached from the image forming apparatus. As the process cartridge, for example, a process cartridge including a developing means containing the electrostatic charge image developer according to the present embodiment is preferably used.

Hereinafter, an example of the image forming apparatus according to the present embodiment will be shown, but the present invention is not limited thereto. The main parts shown in the figure will be described, and the other parts will be omitted.

FIG. 2 is a schematic configuration diagram showing an image forming apparatus according to the present embodiment.
The image forming apparatus shown in FIG. 2 is an electrophotographic first to output images of each color of yellow (Y), magenta (M), cyan (C), and black (K) based on color-separated image data. A fourth image forming unit 10Y, 10M, 10C, 10K (image forming means) is provided. These image forming units (hereinafter, may be simply referred to as “units”) 10Y, 10M, 10C, and 10K are arranged side by side at a predetermined distance from each other in the horizontal direction. The units 10Y, 10M, 10C, and 10K may be process cartridges that are attached to and detached from the image forming apparatus.

An intermediate transfer belt 20 as an intermediate transfer body is extended through each unit above the drawings of each unit 10Y, 10M, 10C, and 10K. The intermediate transfer belt 20 is provided by being wound around a drive roll 22 arranged apart from each other from the left to the right in the drawing and a support roll 24 in contact with the inner surface of the intermediate transfer belt 20, and the first unit 10Y to the fourth unit 10Y to the fourth. It is designed to run in the direction toward the unit 10K. A force is applied to the support roll 24 in a direction away from the drive roll 22 by a spring or the like (not shown), and tension is applied to the intermediate transfer belt 20 wound around the support roll 24. Further, an intermediate transfer body cleaning device 30 is provided on the side surface of the image holder of the intermediate transfer belt 20 so as to face the drive roll 22.
Further, the developing devices (development means) 4Y, 4M, 4C, and 4K of each unit 10Y, 10M, 10C, and 10K each have yellow, magenta, cyan, and black contained in the toner cartridges 8Y, 8M, 8C, and 8K. Toner containing the four colors of toner is supplied.

Since the first to fourth units 10Y, 10M, 10C, and 10K have the same configuration, here, the first unit forming a yellow image arranged on the upstream side in the traveling direction of the intermediate transfer belt. 10Y will be described as a representative. The second to fourth units are provided with reference numerals having magenta (M), cyan (C), and black (K) instead of yellow (Y) in the portion equivalent to the first unit 10Y. The description of the units 10M, 10C, and 10K of the above is omitted.

The first unit 10Y has a photoconductor 1Y that acts as an image holder. Around the photoconductor 1Y, a charging roll (an example of charging means) 2Y that charges the surface of the photoconductor 1Y to a predetermined potential, and a laser beam 3Y based on a color-separated image signal expose the charged surface. An exposure device (an example of a static charge image forming means) 3 for forming an electrostatic charge image, and a developing device (an example of a developing means) 4Y for developing a static charge image by supplying a charged toner to the static charge image. A primary transfer roll 5Y (an example of a primary transfer means) that transfers a toner image onto an intermediate transfer belt 20, and a photoconductor cleaning device (an example of a cleaning means) 6Y that removes toner remaining on the surface of the photoconductor 1Y after the primary transfer. Are arranged in order.
The primary transfer roll 5Y is arranged inside the intermediate transfer belt 20 and is provided at a position facing the photoconductor 1Y. Further, a bias power supply (not shown) for applying a primary transfer bias is connected to each of the primary transfer rolls 5Y, 5M, 5C, and 5K. Each bias power supply changes the transfer bias applied to each primary transfer roll by control by a control unit (not shown).

Hereinafter, the operation of forming a yellow image in the first unit 10Y will be described.
First, prior to the operation, the surface of the photoconductor 1Y is charged to a potential of −600V to −800V by the charging roll 2Y.
The photoconductor 1Y is formed by laminating a photosensitive layer on a conductive substrate (for example, volume resistivity at 20 ° C.: 1 × 10 ^{-6 Ωcm or less).} This photosensitive layer usually has a high resistivity (resistance of a general resin), but has a property that when the laser beam 3Y is irradiated, the specific resistance of the portion irradiated with the laser beam changes. Therefore, the laser beam 3Y is output to the surface of the charged photoconductor 1Y via the exposure device 3 according to the image data for yellow sent from the control unit (not shown). The laser beam 3Y irradiates the photosensitive layer on the surface of the photoconductor 1Y, whereby an electrostatic charge image of a yellow image pattern is formed on the surface of the photoconductor 1Y.

The static charge image is an image formed on the surface of the photoconductor 1Y by charging. The laser beam 3Y reduces the specific resistance of the irradiated portion of the photosensitizer layer, and the charged charge on the surface of the photoconductor 1Y flows. On the other hand, it is a so-called negative latent image formed by the residual charge of the portion not irradiated with the laser beam 3Y.
The electrostatic charge image formed on the photoconductor 1Y is rotated to a predetermined development position as the photoconductor 1Y travels. Then, at this developing position, the electrostatic charge image on the photoconductor 1Y is converted into a visible image (developed image) as a toner image by the developing device 4Y.

In the developing apparatus 4Y, for example, a static charge image developing agent containing at least yellow toner and a carrier is housed. The yellow toner is triboelectrically charged by being agitated inside the developing apparatus 4Y, and has a charge having the same polarity (negative electrode property) as the charged charge on the photoconductor 1Y, and is a developer roll (developing agent holder). Example) It is held on. Then, as the surface of the photoconductor 1Y passes through the developing device 4Y, the yellow toner is electrostatically adhered to the statically eliminated latent image portion on the surface of the photoconductor 1Y, and the latent image is developed by the yellow toner. .. The photoconductor 1Y on which the yellow toner image is formed is continuously traveled at a predetermined speed, and the toner image developed on the photoconductor 1Y is conveyed to a predetermined primary transfer position.

When the yellow toner image on the photoconductor 1Y is transferred to the primary transfer, a primary transfer bias is applied to the primary transfer roll 5Y, and an electrostatic force from the photoconductor 1Y toward the primary transfer roll 5Y is applied to the toner image to act on the photoconductor. The toner image on 1Y is transferred onto the intermediate transfer belt 20. The transfer bias applied at this time has a polarity (+) opposite to the polarity (−) of the toner, and is controlled to +10 μA by the control unit (not shown) in the first unit 10Y, for example.
On the other hand, the toner remaining on the photoconductor 1Y is removed by the photoconductor cleaning device 6Y and recovered.

Further, the primary transfer bias applied to the primary transfer rolls 5M, 5C, and 5K after the second unit 10M is also controlled according to the first unit.
In this way, the intermediate transfer belt 20 to which the yellow toner image is transferred in the first unit 10Y is sequentially conveyed through the second to fourth units 10M, 10C, and 10K, and the toner images of each color are superimposed and multiplex transferred. Toner.

The intermediate transfer belt 20 on which four color toner images are multiplex-transferred through the first to fourth units is arranged on the image holding surface side of the intermediate transfer belt 20, the support roll 24 in contact with the inner surface of the intermediate transfer belt, and the intermediate transfer belt 20. It leads to a secondary transfer unit composed of the secondary transfer roll (an example of the secondary transfer means) 26. On the other hand, the recording paper (an example of the recording medium) P is fed through the supply mechanism into the gap where the secondary transfer roll 26 and the intermediate transfer belt 20 are in contact with each other at a predetermined timing, and the secondary transfer bias is supported by the support roll. It is applied to 24. The transfer bias applied at this time has a (-) polarity that is the same as the polarity (-) of the toner, and an electrostatic force from the intermediate transfer belt 20 toward the recording paper P is applied to the toner image, so that the intermediate transfer belt 20 is on. The toner image of is transferred onto the recording paper P. The secondary transfer bias at this time is determined according to the resistance detected by the resistance detecting means (not shown) for detecting the resistance of the secondary transfer unit, and is voltage controlled.

After that, the recording paper P is sent to the pressure contact portion (nip portion) of the pair of fixing rolls in the fixing device (an example of the fixing means) 28, and the toner image is fixed on the recording paper P to form the fixing image.

Examples of the recording paper P for transferring the toner image include plain paper used in electrophotographic copiers, printers, and the like. Examples of the recording medium include an OHP sheet and the like in addition to the recording paper P.
In order to further improve the smoothness of the image surface after fixing, the surface of the recording paper P is also preferably smooth, and for example, coated paper in which the surface of plain paper is coated with resin or the like, art paper for printing, or the like is preferably used. Will be done.

The recording paper P for which the color image has been fixed is carried out toward the discharge unit, and a series of color image forming operations is completed.

<Process Cartridge / Toner Cartridge>
The process cartridge according to this embodiment will be described.
The process cartridge according to the present embodiment contains the electrostatic charge image developer according to the present embodiment, and is a developing means for developing the electrostatic charge image formed on the surface of the image holder as a toner image by the electrostatic charge image developer. It is a process cartridge that is attached to and detached from the image forming apparatus.

The process cartridge according to the present embodiment is not limited to the above configuration, and includes a developing device and other means such as an image holder, a charging means, an electrostatic charge image forming means, and a transfer means, if necessary. It may be configured to include at least one selected from.

Hereinafter, an example of the process cartridge according to the present embodiment will be shown, but the present invention is not limited thereto. The main parts shown in the figure will be described, and the other parts will be omitted.

FIG. 3 is a schematic configuration diagram showing a process cartridge according to the present embodiment.
The process cartridge 200 shown in FIG. 3 is provided around the photoconductor 107 (an example of an image holder) and the photoconductor 107 by, for example, a housing 117 provided with a mounting rail 116 and an opening 118 for exposure. The charged roll 108 (an example of the charging means), the developing device 111 (an example of the developing means), and the photoconductor cleaning device 113 (an example of the cleaning means) are integrally combined and held and configured to form a cartridge. There is.
In FIG. 3, 109 is an exposure device (an example of an electrostatic charge image forming means), 112 is a transfer device (an example of a transfer means), 115 is a fixing device (an example of a fixing means), and 300 is a recording paper (an example of a recording medium). An example) is shown.

Next, the toner cartridge according to this embodiment will be described.
The toner cartridge according to the present embodiment is a toner cartridge that houses the toner according to the present embodiment and is attached to and detached from the image forming apparatus. The toner cartridge accommodates a replenishing toner for supplying to the developing means provided in the image forming apparatus.

The image forming apparatus shown in FIG. 2 is an image forming apparatus having a structure in which the toner cartridges 8Y, 8M, 8C, and 8K are attached and detached, and the developing apparatus 4Y, 4M, 4C, and 4K are each developing apparatus (color). ) Is connected to a toner cartridge (not shown). When the amount of toner contained in the toner cartridge is low, the toner cartridge is replaced.

Hereinafter, examples of the present invention will be described, but the present invention is not limited to the following examples. In the following description, unless otherwise specified, "parts" and "%" are all based on mass.

<Measurement of sulfur atom content and alkali metal atom content in resin particles in resin particle dispersion>
50 g of the resin particle dispersion is sealed in a dialysis membrane (Dialesis membrane, size 36, manufactured by Wako Pure Chemical Industries, Ltd.) and immersed in 10 L of pure water for 5 days with stirring (pure water is replaced every day). Impurities in the dispersion were removed. Then, the resin particle dispersion liquid subjected to the dialysis treatment was dried using a freeze dryer. Using a fluorescent X-ray analyzer (scanning fluorescent X-ray analyzer, ZSX PrimusII, manufactured by Rigaku Co., Ltd.), the net strength of the sulfur atomic weight and alkali metal atomic weight contained in the dried resin particles was measured. , The atomic weight of sulfur and the atomic weight of alkali metal in the resin particles were calculated from the calibration curve prepared in advance. As a sample pretreatment, 0.1 g to 0.2 g of dried resin particles are disc-molded by pressure molding, and the measurement conditions are qualitative quantitative measurement, tube voltage 40 kV, tube current 70 mA, measurement time 15 minutes. It was measured.

(Example 1)
<Preparation of resin particle dispersion (a1)>
Amorphous polyester resin (acid value: 14.9 mgKOH / g, glass transition temperature (Tg): 60 ° C., melting point (Tm): 110 ° C.) 192 parts by mass, crystalline polyester resin 8 parts by mass, sodium hydroxide 20 parts by mass 4 parts by mass of% aqueous solution was put into the raw material inlet of the twin-screw extruder (trade name: TEM26SS, manufactured by Toshiba Machine Co., Ltd.), and dodecylbenzene as a surfactant from the fourth barrel of the twin-screw extruder. 60 parts by mass of a 10 mass% aqueous solution of sodium sulfonate (Neoperex G-15 manufactured by Kao Co., Ltd.) was added and melted at a barrel temperature of 90 ° C. and a screw rotation speed of 200 rpm (revolutions per minute) to prepare an oily mixture. The resin particle dispersion liquid manufacturing apparatus is shown in FIG.
100 parts by mass of pure water (pure water 1) adjusted to 90 ° C from the 5th barrel of the twin-screw extruder, 100 parts by mass of pure water (pure water 2) adjusted to 90 ° C from the 7th barrel, 9th barrel 100 parts by mass of pure water (pure water 3) adjusted to 90 ° C. was added, and the oily mixture was emulsified to obtain a resin particle dispersion liquid (a1).
The volume average particle size distribution of the particles in the obtained resin particle dispersion was measured by a laser diffraction type particle size distribution measuring machine (LA-700, manufactured by HORIBA, Ltd.). As a result, the volume average particle size distribution (GSDv = √ (D84v / D16v)) of the resin particles was 1.25.

<Preparation of mold release agent dispersion>
-Release agent (manufactured by Nippon Seiwa Co., Ltd., trade name: FNP0090, melting point Tw89.7 ° C): 270 parts by mass-Anionic surfactant (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., Neogen RK, amount of active ingredient : 60% by mass): 13.5 parts by mass (3.0% by mass as an active ingredient with respect to the release agent)
-Ion-exchanged water: 721.6 parts by mass After mixing the above components and dissolving the release agent with a pressure discharge type homogenizer (Gorin homogenizer manufactured by Gorin) at an internal liquid temperature of 120 ° C., the dispersion pressure is 5 MPa. Then, the mixture was dispersed at 40 MPa for 360 minutes and cooled to obtain a release agent dispersion. The volume average particle diameter D50v of the particles in this dispersion was 230 nm. Then, ion-exchanged water was added to adjust the solid content concentration to 20.0% by mass to obtain a release agent dispersion.

<Preparation of colorant dispersion>
-Cyan pigment (manufactured by Dainichi Seika Kogyo Co., Ltd .: ECB 301): 200 parts by mass-Anionic surfactant (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., Neogen SC): 33 parts by mass (active ingredient 60% by mass). 10% by mass with respect to the colorant)
-Ion-exchanged water: 750 parts by mass Ion-exchanged water is anionic with 280 parts by mass in a stainless steel container whose size is such that the height of the liquid level becomes about 1/3 of the height of the container when all the above components are charged. After adding 33 parts by mass of the surfactant and sufficiently dissolving the surfactant, all the cyan pigments are added, and the mixture is stirred using a stirrer until there are no wet pigments, and the bubbles are sufficiently defoamed. It was. After defoaming, the remaining ion-exchanged water was added, and the mixture was dispersed at 5,000 rpm for 10 minutes using a homogenizer (Ultratarax T50 manufactured by IKA), and then defoamed by stirring with a stirrer for 1 day and night. After defoaming, the mixture was dispersed again at 6,000 rpm for 10 minutes using a homogenizer, and then defoamed by stirring with a stirrer for 1 day and night. Subsequently, the dispersion was dispersed at a pressure of 240 MPa using a high-pressure impact disperser Ultimateizer (HJP30006, manufactured by Sugino Machine Limited). Dispersion was performed equivalent to 10 passes in terms of the total charge amount and the processing capacity of the apparatus. The obtained dispersion was left to stand for 72 hours to remove the precipitate, and ion-exchanged water was added to adjust the solid content concentration to 15% by mass. The volume average particle size D50v of the particles in this colorant dispersion was 115 nm. For the volume average particle diameter D50v, the average value of the three measured values excluding the maximum value and the minimum value among the five times measured with the microtrack was used.

<Preparation of aqueous solution of aluminum sulfate>
-Aluminum sulfate powder (manufactured by Asada Chemical Industry Co., Ltd .: 17% by mass aluminum sulfate): 35 parts-Ion-exchanged water: 1,965 parts Put the powder and ion-exchanged water into a container and precipitate at 30 ° C. An aqueous solution of aluminum sulfate as a coagulant was prepared by stirring and mixing until the substance disappeared.

<Adjustment of toner component dispersion>
Each of the following components was placed in a stirring tank equipped with a thermometer, a pH meter, a stirrer and a jacket, and stirred for 10 minutes.
-Resin particle dispersion (a1): 600 parts-Colorant dispersion: 100 parts-Release release agent dispersion: 115 parts-Ion-exchanged water: 200 parts-Anionic surfactant 10% by mass (manufactured by Kao Corporation) , Neoperex G-15): 53 copies

<Manufacturing of toner>
-Agglomeration process-
While gradually adding 125 parts by mass of an aqueous aluminum sulfate solution to the dispersion liquid mixture placed in the stirring tank, the mixed liquid was introduced into Cavitron CD1010 (manufactured by Eurotech Co., Ltd.) from the bottom valve of the stirring tank and dispersed for 10 minutes. did. After the addition was completed, the temperature of the jacket was started to be raised at 50 ° C., and after 120 minutes, the particle size was measured with Multisizer II (aperture diameter: 50 μm, manufactured by Beckman-Coulter). It was 5.0 μm. Then, 312 parts by mass of the additional resin particle dispersion liquid (a1) was added and held for 30 minutes.

-Fusion process-
A 4 mass% sodium hydroxide aqueous solution was added to the stirring tank to adjust the pH to 7.0, and then the temperature of the jacket was raised to 90 ° C. and maintained. When the shape and surface properties of the agglomerated particles were observed with an optical microscope and a field emission scanning electron microscope (FE-SEM) every 30 minutes, coalescence of the particles was confirmed at 4 hours, so the results were obtained. The slurry was cooled to 40 ° C. The cooled slurry was sieved with a vibrating sieve (KGC800, manufactured by Kowa Kogyo Co., Ltd.) having an opening of 15 μm, and then filtered with a filter press (manufactured by Tokyo Engineering Co., Ltd.). Then, ion-exchanged water 10 times the amount of toner was passed through the toner in the filter press device to wash the toner. The washed toner was dried by cyclone collection using a loop type airflow dryer (Flash Jet Dryer FJD-2 manufactured by Seishin Co., Ltd.) to obtain toner particles.

With respect to 100 parts by mass of the obtained toner particles, 1.0 part by mass of hydrophobic silica (manufactured by Nippon Aerodil Co., Ltd., RY50) and 0.8 parts by mass of hydrophobic titanium oxide (manufactured by Nippon Aerozil Co., Ltd., T805). Was added, and the mixture was mixed and blended at 13,000 rpm for 30 seconds using a sample mill. Then, it was sieved with a vibrating sieve having an opening of 45 μm to obtain a toner (toner for developing an electrostatic charge image).

<Measurement of sulfur atom content and alkali metal atom content in toner>
Using a fluorescent X-ray analyzer (scanning fluorescent X-ray analyzer, ZSX PrimusII), the toner produced by the above method has the net strength of the sulfur atom content and the alkali metal atom content in the toner. Was measured, and the content of sulfur atoms and the content of alkali metal atoms in the toner were calculated from the calibration curve prepared in advance. As a sample pretreatment, 0.1 g to 0.2 g of dried toner is disk-molded by pressure molding, and the measurement conditions are qualitative quantitative measurement, tube voltage 40 kV, tube current 70 mA, and measurement time 15 minutes. did.

<Creation of carrier>
-Mn-Mg-Sr-based ferrite particles (average particle size 40 μm): 100 parts-Toluene: 14 parts-Cyclohexyl methacrylate / dimethylaminoethyl methacrylate copolymer (copolymerization mass ratio 99: 1, weight average molecular weight Mw 80,000) : 2.0 parts-Carbon black (VXC72: manufactured by Cabot): 0.12 parts The above components excluding ferrite particles and glass beads (φ1 mm, the same amount as toluene) are 1 using a sand mill manufactured by Kansai Paint Co., Ltd. , 200 ppm for 30 minutes to prepare a resin coating layer forming solution. Further, the resin coating layer forming solution and the ferrite particles were placed in a vacuum degassing type kneader to reduce the pressure, and toluene was distilled off / dried to form a resin coating carrier.

<Preparation of developer>
40 parts by mass of the toner is added to 500 parts by mass of the carrier, blended with a V-type blender for 20 minutes, and then aggregates are removed by a vibrating sieve having a mesh size of 212 μm to remove the developer (A1) (static charge image developer). ) Was obtained.

<Evaluation of transfer efficiency (evaluation of transferability)>
The obtained electrostatic charge image developer was filled in a developer of a Docu Center Color 400 remodeling machine (manufactured by Fuji Xerox Co., Ltd.), and the transfer efficiency was evaluated.
The transfer efficiency was evaluated as follows. As a test procedure, first, the developing potential was adjusted so that the toner loading amount on the photoconductor was 5 g / m ^{2 in an environment of temperature 10 ° C./humidity 20% RH.} Next, the evaluation machine is stopped immediately after the developed toner on the photoconductor is transferred to the intermediate transfer body (intermediate transfer belt). As a result, the toner remains on the photoconductor in the state after transfer (before cleaning). This toner is taken with a mending tape and the toner mass at that time is measured. The transfer efficiency was determined based on the following equation from the ratio of the toner loading amount during development (toner loading amount on the photoconductor during development) and the toner loading amount after transfer (toner loading amount on paper after transfer). The transfer efficiency was measured after continuously outputting 50,000 sheets of A4 paper with an image having an image area of 5%.
-Formula: Transfer efficiency = Toner transfer amount on paper after transfer / Toner transfer amount on photoconductor during development x 100
The evaluation criteria for transfer efficiency are as follows. The higher the transfer efficiency, the better the transferability.
A: Transcription efficiency 98% or more B: Transcription efficiency 95% or more and less than 98% C: Transcription efficiency 90% or more and less than 95% D: Transcription efficiency 85% or more and less than 90% E: Transcription efficiency less than 85%

<Cold offset evaluation (fixability evaluation)>
The obtained electrostatic charge image developer was filled in a developer of a color copier Docu Center Color 400 (manufactured by Fuji Xerox Co., Ltd.) from which the fuser was taken out so that the toner loading amount was 0.45 mg / cm ^2. After adjustment, an unfixed image was output. As a recording medium, SP paper A4 size (basis weight 60 g / m ² ) manufactured by Fuji Xerox Co., Ltd. is used, and the output image has an image density of 50 mm × 50 mm and an image density of 100%, 50%, 25%, 10%. It is an image.
As the fixing evaluation device, a fixing device of ApeosPortIV C3370 manufactured by Fuji Xerox Co., Ltd. was removed and modified so that the fixing temperature could be changed. The nip width of the fuser was 6 mm, the nip pressure was 1.6 kgf / cm ² , the Dwell time (contact time) was 34.7 ms, and the process speed was 175 mm / sec.
The unfixed image was fixed at intervals of 2 ° C. from the fixing temperature of 130 ° C., the presence or absence of cold offset was visually confirmed, and the maximum temperature at which the cold offset occurred was evaluated as the cold offset generation temperature. The evaluation criteria are shown below. The lower the cold offset generation temperature, the better the fixability.
A: Cold offset generation temperature is less than 150 ° C B: Cold offset generation temperature is 150 ° C or more and less than 160 ° C C: Cold offset generation temperature is 160 ° C or more and less than 170 ° C D: Cold offset generation temperature is 170 ° C or more

(Examples 2 to 14)
After obtaining a developer in the same manner as in Example 1 except that the types and amounts of the resin, surfactant, and basic compound used were changed as shown in Table 1, the evaluation was carried out in the same manner.

(Example 15)
<Preparation of resin particle dispersion (a2)>
Amorphous polyester resin (acid value: 14.9 mgKOH / g, glass transition temperature (Tg): 60 ° C., melting point (Tm): 110 ° C.) 192 parts by mass, crystalline polyester resin 8 parts by mass, cyan pigment (Dainichisei) Chemical Industry Co., Ltd .: ECB 301) 15 parts by mass and sodium hydroxide 20% by mass aqueous solution 4 parts by mass are put into the raw material inlet of a twin-screw extruder (trade name: TEM26SS, manufactured by Toshiba Machinery Co., Ltd.). Also, from the 4th barrel of the twin-screw extruder, sodium dodecylbenzene sulfonate (manufactured by Kao Co., Ltd., Neoperex G-15) and sodium alkyldiphenyl ether disulfonate (manufactured by Kao Co., Ltd., Perex) are used as surfactants. 60 parts by mass of a 10 mass% aqueous solution of the mixture of SS—H) was added and melted at a barrel temperature of 90 ° C. and a screw rotation speed of 200 rpm to prepare an oily mixture.
100 parts by mass of pure water (pure water 1) adjusted to 90 ° C from the 5th barrel of the twin-screw extruder, 100 parts by mass of pure water (pure water 2) adjusted to 90 ° C from the 7th barrel, 9th barrel 100 parts by mass of pure water (pure water 3) adjusted to 90 ° C. was added, and the oily mixture was emulsified to obtain a resin particle dispersion liquid (a1).
The volume average particle size distribution of the particles in the obtained resin particle dispersion was measured by a laser diffraction type particle size distribution measuring machine (LA-700, manufactured by HORIBA, Ltd.). As a result, the volume average particle size distribution (GSDv = √ (D84v / D16v)) of the resin particles was 1.28.
After that, the colorant dispersion is not adjusted, and the resin particle dispersion (a2) is used instead of the resin particle dispersion (a1) in the step of adjusting the toner component dispersion, except that the colorant dispersion is not added. After obtaining a developer in the same manner as in Example 1, the evaluation was carried out in the same manner.

(Comparative Example 1)
<Preparation of resin particle dispersion (a3)>
200 parts by mass of amorphous polyester resin (acid value: 14.9 mgKOH / g, glass transition temperature (Tg): 60 ° C., melting point (Tm): 110 ° C.), 4 parts by mass of sodium hydroxide 20% by mass aqueous solution, 2 parts. The shaft extruder (trade name: TEM26SS, manufactured by Toshiba Machine Co., Ltd.) is charged into the raw material inlet, and from the 4th barrel of the twin shaft extruder, sodium dodecylbenzene sulfonate (Kao Co., Ltd.) is used as a surfactant. 60 parts by mass of a 10 mass% aqueous solution of a mixture of Neoperex G-15) and sodium alkyldiphenyl ether disulfonate (Perex SS-H manufactured by Kao Co., Ltd.) was added, the barrel temperature was 90 ° C., and the screw rotation speed was 200 rpm. To prepare an oily mixture. The resin particle dispersion liquid manufacturing apparatus is shown in FIG.
100 parts by mass of pure water (pure water 1) adjusted to 90 ° C from the 5th barrel of the twin-screw extruder, 100 parts by mass of pure water (pure water 2) adjusted to 90 ° C from the 7th barrel, 9th barrel 100 parts by mass of pure water (pure water 3) adjusted to 90 ° C. was added, and the oily mixture was emulsified to obtain a resin particle dispersion liquid (a1).
The volume average particle size distribution of the particles in the obtained resin particle dispersion was measured by a laser diffraction type particle size distribution measuring machine (LA-700, manufactured by HORIBA, Ltd.). As a result, the volume average particle size distribution (GSDv = √ (D84v / D16v)) of the resin particles was 1.45.

<Preparation of resin particle dispersion (a4)>
200 parts by mass of crystalline polyester resin is placed in 800 parts by mass of distilled water, heated to 85 ° C., adjusted to pH 9.0 with ammonia, and anionic surfactant (Neogen RK manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). ) 0.4 parts by mass (as an active ingredient) was added and dispersed at 8000 rpm for 7 minutes with a homogenizer (Ultratarax T50 manufactured by IKA Japan) while heating at 85 ° C. to obtain a resin particle dispersion (a4). Got

After that, in the step of adjusting the dispersion liquid of the toner components, the amount of each component added is: -Resin particle dispersion liquid (a3): 576 parts-Resin particle dispersion liquid (a4): 48 parts-Colorant dispersion liquid: 100 parts-Release Agent dispersion: 115 parts ・ Ion-exchanged water: 200 parts ・ Anionic surfactant 10% by mass (manufactured by Kao Corporation, Neoperex G-15): 53 parts in the same manner as in Example 1. After obtaining the developer, the evaluation was carried out in the same manner.

(Comparative Example 2 to Comparative Example 5)
After obtaining a developer in the same manner as in Example 1 except that the types and amounts of the resin, surfactant, and basic compound used were changed as shown in Table 1, the evaluation was carried out in the same manner.

The evaluation results are summarized in Table 1.

The details of the abbreviations in Table 1 are shown below.
S-1: Sodium alkyl diphenyl ether disulfonate (manufactured by Kao Corporation, Perex SS-H)
S-2: Sodium dodecylbenzenesulfonate (manufactured by Kao Corporation, Neoperex G-15)
S-3: A mixture of S-1 and S-2 with a mass ratio of 1: 1.

From the results shown in Table 1 above, the method for producing the resin particle dispersion liquid and the resin particle dispersion liquid of this example have a fixability in the obtained toner as compared with the method for producing the resin particle dispersion liquid and the resin particle dispersion liquid of the comparative example. And it can be seen that the transferability is excellent.

1Y, 1M, 1C, 1K photoconductor (example of image holder)
2Y, 2M, 2C, 2K charging roll (an example of charging means)
3 Exposure device (an example of static charge image forming means)
3Y, 3M, 3C, 3K laser beam 4Y, 4M, 4C, 4K developing device (example of developing means)
5Y, 5M, 5C, 5K primary transfer roll (example of primary transfer means)
6Y, 6M, 6C, 6K Photoreceptor cleaning device (an example of image holder cleaning means)
8Y, 8M, 8C, 8K Toner Cartridge 10Y, 10M, 10C, 10K Image Forming Unit 20 Intermediate Transfer Belt (Example of Intermediate Transfer)
22 Drive roll 24 Support roll 26 Secondary transfer roll (an example of secondary transfer means)
28 Fixing device (an example of fixing means)
30 Intermediate transfer belt cleaning device (an example of intermediate transfer body cleaning means)
P Recording paper (an example of recording medium)

107 Photoreceptor (an example of image holder)
108 Charging roll (an example of charging means)
109 Exposure device (an example of static charge image forming means)
111 Developing equipment (an example of developing means)
112 Transfer device (an example of transfer means)
113 Photoreceptor cleaning device (an example of image holder cleaning means)
115 Fixing device (an example of fixing means)
116 Mounting rail 117 Housing 118 Opening for exposure 200 Process cartridge 300 Recording paper (an example of recording medium)

210 Biaxial extruder 212 Cylinder 214 Raw material inlet 216 Base aqueous solution inlet 218 Surfactant inlet 220, 221,222 Water inlet 224 Outlet 226 Supply line 228 Pump 230 Resin feeder 232 Base aqueous solution tank 234 Surfactant Aqueous solution tank 236 Temperature controller 238 Pure water tank 240 Heater 242 Resin supply barrel 244 Cylinder part other than resin supply barrel 242

Claims (15)

A melting step of adding a surfactant and a basic compound to a resin mixture containing an amorphous resin and a crystalline resin in the absence of an organic solvent to obtain a melt mixture while applying shearing force.
It includes an emulsification step of adding an aqueous medium and emulsifying the molten mixture while applying shearing force.
The content of the surfactant in the molten mixture is 1% by mass or more and 5% by mass or less with respect to the total mass of the resin in the molten mixture.
A method for producing a resin particle dispersion, wherein the content of the basic compound in the molten mixture is 0.05 mol or more and 0.2 mol or less with respect to 1 kg of the resin in the molten mixture. The method for producing a resin particle dispersion according to claim 1, wherein the content of the crystalline resin in the molten mixture is 2% by mass or more and 15% by mass or less with respect to the total mass of the molten mixture. The method for producing a resin particle dispersion according to claim 1 or 2, wherein the surfactant contains two or more kinds of surfactants. The method for producing a resin particle dispersion according to claim 3, wherein the two or more kinds of surfactants contain two or more kinds of anionic surfactants. The method for producing a resin particle dispersion according to claim 4, wherein the two or more anionic surfactants contain an alkylbenzene sulfonate compound and a disulfonate compound having a monoalkyldiphenyl ether structure. The production of the resin particle dispersion liquid according to any one of claims 1 to 5, wherein the content of sulfur atoms in the resin particles in the resin particle dispersion liquid is 0.03% by mass or more and 1% by mass or less. Method. The method for producing a resin particle dispersion liquid according to claim 6, wherein the content of sulfur atoms in the resin particles in the resin particle dispersion liquid is 0.06% by mass or more and 0.6% by mass or less. The resin particle dispersion according to any one of claims 1 to 7, wherein the content of the alkali metal atom in the resin particles in the resin particle dispersion liquid is 0.1% by mass or more and 1.5% by mass or less. Liquid manufacturing method. The method for producing a resin particle dispersion liquid according to claim 8, wherein the content of the alkali metal atom in the resin particles in the resin particle dispersion liquid is 0.15% by mass or more and 1% by mass or less. Claims 1 to 9 in which the weight average molecular weight of the crystalline resin in the melt mixture is smaller than the weight average molecular weight of at least one peak in the molecular weight distribution of the amorphous resin in the melt mixture. The method for producing a resin particle dispersion liquid according to any one of the above items. The method for producing a resin particle dispersion liquid according to any one of claims 1 to 10, wherein the melt mixture contains a pigment. The method for producing a resin particle dispersion liquid according to any one of claims 1 to 11, wherein the amorphous resin is an amorphous polyester resin and the crystalline resin is a crystalline polyester resin. The agglomeration step of forming agglomerated particles containing resin particles,
Including a fusion step of forming toner particles by fusing the agglomerated particles.
Production of Toner for Static Charge Image Development, wherein the resin particles contain resin particles contained in the resin particle dispersion liquid produced by the method for producing a resin particle dispersion liquid according to any one of claims 1 to 12. Method. The charging process that charges the surface of the image holder,
A static charge image forming step of forming a static charge image on the surface of the charged image holder, and
A developing step of developing a static charge image formed on the surface of the image holder as a toner image with a static charge image developer containing toner.
A transfer step of transferring a toner image formed on the surface of the image holder to the surface of a recording medium, and
It has a fixing step of fixing the toner image transferred to the surface of the recording medium.
An image forming method in which the toner contains the toner produced by the method for producing an electrostatic charge image developing toner according to claim 13. Contains resin particles containing amorphous resins, crystalline resins, surfactants, and basic compounds.
The content of the surfactant is 1% by mass or more and 5% by mass or less with respect to the total mass of the resin particles.
The content of the basic compound in the resin particle dispersion is 0.05 mol or more and 0.2 mol or less with respect to 1 kg of the resin in the resin particle dispersion.
The content of sulfur atoms in the resin particles is 0.03% by mass or more and 1% by mass or less.
A resin particle dispersion having an alkali metal atom content of 0.1% by mass or more and 1.5% by mass or less in the resin particles.

Images