JP2016164612A - Toner and developer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner that maintains good quality of the toner, is excellent in pigment dispersibility, has desired circularity, and is excellent in cleaning property, the toner capable of providing good images for a long period.SOLUTION: There is provided a toner containing at least a colorant, binder resin, and mold release agent, where the binder resin contains a polyester resin; an acid monomer constituting the polyester resin includes a sulfo-substituted benzene dicarboxylic acid metal salt; the average circularity of the toner is 0.940 to 0.970.SELECTED DRAWING: None

Description

  The present invention relates to a toner for image formation and a developer containing the toner.

  In recent years, toners have been able to withstand high temperature and high humidity during storage and transportation after production, as well as reduction in particle size for high quality output images, high temperature offset resistance, low temperature fixability for energy saving. High heat-resistant storage stability is required. In particular, since power consumption during fixing accounts for much of the power consumption in the image forming process, it is very important to improve low-temperature fixability.

Conventionally, toner prepared by a kneading and pulverizing method has been used. The toner produced by the kneading and pulverization method is difficult to reduce the particle size, the shape is irregular and the particle size distribution is broad, so the quality of the output image is not sufficient, and the fixing energy is high. There were problems such as. In addition, when a wax (release agent) is added to improve the fixability, the toner produced by the kneading and pulverization method cracks at the interface of the wax during pulverization, so that a large amount of wax exists on the toner surface. Resulting in. For this reason, there is a problem in that, while the releasing effect is produced, the toner (filming) easily adheres to the carrier, the photoreceptor and the blade, and the overall performance is not satisfactory.
Therefore, in order to overcome the above-mentioned problems caused by the kneading and pulverizing method, a toner manufacturing method by a polymerization method has been proposed. The toner produced by the polymerization method can be easily reduced in particle size, the particle size distribution is sharper than that of the toner produced by the pulverization method, and the release agent can be included. . As a method for producing a toner by a polymerization method, for the purpose of improving low-temperature fixability and improving high-temperature offset resistance, a method of producing a toner from an extension reaction product of urethane-modified polyester as a toner binder is disclosed. (For example, refer to Patent Document 1).
However, since these polymerization methods are granulated in water, the pigment dispersibility inside the resulting toner is poor due to the hydrophilicity of the pigment and the low affinity between the pigment and the resin, and the pigment is unevenly distributed in the vicinity of the toner surface layer. In some cases, the color reproducibility and fixing characteristics are often adversely affected.

In order to disperse the pigment in the toner obtained by the polymerization method, a method of improving the pigment dispersibility inside the toner using a pigment dispersant or the like has been proposed (for example, see Patent Documents 2, 3, and 4). ).
However, in the methods described in these documents, the pigment dispersibility improvement in the toner obtained by the polymerization method is insufficient, and it is difficult to suppress aggregation and uneven distribution of pigment particles near the toner surface. .
In order to improve the dispersibility of the pigment in the toner, a method of introducing a polar group into an acid monomer constituting an amorphous polyester resin has been proposed (see, for example, Patent Document 5).

According to the method described in Patent Document 5, it is possible to suppress pigment dispersibility in the toner, aggregation and uneven distribution of pigment particles in the vicinity of the toner surface, but toner particles are insufficiently deformed and have poor cleaning properties. There was a problem.
Accordingly, there is a demand for a toner excellent in cleaning properties having a desired circularity by being excellent in pigment dispersibility and appropriately deforming the shape of toner particles.
The present invention provides a toner that is excellent in pigment dispersibility, has a desired circularity, and is excellent in cleaning properties while maintaining good toner quality, and can obtain a good image over a long period of time. With the goal.

Means for solving the problems are as follows. That is, the toner of the present invention is a toner containing at least a colorant, a binder resin and a release agent.
The binder resin contains a polyester resin,
The polyester resin, the constituent acid monomer comprises a sulfo-substituted benzene dicarboxylic acid metal salt,
The toner has an average circularity of 0.940 to 0.970.

  According to the present invention, the conventional problems can be solved, the object can be achieved, the toner dispersibility is excellent, the pigment dispersibility is excellent, and the desired circularity is excellent and the cleaning property is excellent. It is possible to provide a toner capable of obtaining a good image over a long period of time.

(toner)
The toner of the present invention contains at least a colorant, a binder resin, and a release agent, and further includes a charge control agent, an external additive, a fluidity improver, a cleaning property improver, a magnetic material, and the like as necessary. You may contain.

<Binder resin>
The binder resin contains a polyester resin, and the acid monomer constituting the polyester resin contains a sulfo-substituted benzenedicarboxylic acid metal salt.
The polyester resin preferably contains an amorphous polyester resin and a crystalline polyester resin. The amorphous polyester resin preferably contains at least three types of amorphous polyester resins A, B, and C. Furthermore, as at least three kinds of amorphous polyester resins, a modified polyester resin A having a non-linear branched structure and having a urethane bond or a urea bond, and linear unmodified polyester resins B and C are contained. More preferably.

By using amorphous polyester resin A with a very low glass transition temperature, it has the property of being deformed at low temperatures, deformed by heating and pressurization at the time of fixing, and easily adheres to paper at lower temperatures. . Further, when the amorphous polyester resin A has a urethane bond or a urea bond having a high cohesive energy, the adhesiveness to paper is excellent. In addition, the amorphous polyester resin A having a branched structure has a branched structure in the toner molecular skeleton, and a urethane bond or urea bond site having a high cohesive energy behaves like a pseudo-crosslinking point. It has an original network structure and has a rubbery property that it deforms at low temperatures but does not flow. Therefore, it is possible to maintain the heat resistant storage stability and high temperature offset property of the toner.
In other words, toner is obtained by combining amorphous polyester resin A having a glass transition temperature in an ultra-low temperature range but having high melt viscosity and being difficult to flow with other amorphous polyester resins B and C in a compatible state. Even if the glass transition temperature is set low, it is possible to maintain heat resistant storage stability and offset resistance, and it is possible to achieve both low temperature fixability.

<< Amorphous Polyester Resin A >>
The amorphous polyester resin A having a non-linear urethane bond or urea bond will be described.
The amorphous polyester resin A is composed of a non-linear reactive precursor a and a curing agent. The reactive precursor a is a polyester having a reactive site such as isocyanate at the terminal, and is particularly preferably a terminal NCO product of a polyester-based polyurethane.

The amorphous polyester resin A of the present invention preferably has a glass transition temperature of −60 ° C. or higher and lower than 0 ° C. by a glass transition temperature measuring method described later. When the temperature is −60 ° C. or higher, it is possible to prevent the problem that the flow of the toner at a low temperature cannot be suppressed and the heat resistant storage stability is deteriorated. When the temperature is less than 0 ° C., it is possible to prevent the problem that the toner is not sufficiently deformed by heating and pressurization during fixing and the low-temperature fixability is deteriorated.
The amorphous polyester resin A is obtained using a diol component, a dicarboxylic acid, and a trivalent or higher acid or alcohol that imparts a branched structure.

-Diol-
The diol is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 3-methyl Aliphatic diols such as 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol; diethylene glycol, triethylene glycol, dipropylene glycol Diols having an oxyalkylene group such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol; alicyclic diols such as 1,4-cyclohexanedimethanol and hydrogenated bisphenol A; alicyclic diols, ethylene oxide, propylene Bisphenols such as bisphenol A, bisphenol F and bisphenol S; bisphenols such as those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide and butylene oxide to bisphenols Alkylene oxide adducts; and the like. Among these, in order to make it easy to impart a property of low Tg and deformation at low temperatures, it is preferable to contain an aliphatic diol having 4 to less than 12 carbon atoms in an amount of 50% by mass or more based on the total diol component.

-Dicarboxylic acid-
There is no restriction | limiting in particular as said dicarboxylic acid, According to the objective, it can select suitably, For example, aliphatic dicarboxylic acid, aromatic dicarboxylic acid, etc. are mentioned.
The aliphatic dicarboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include succinic acid, adipic acid, sebacic acid, dodecanedioic acid, maleic acid, and fumaric acid.
There is no restriction | limiting in particular as said aromatic dicarboxylic acid, Although it can select suitably according to the objective, C8-C20 aromatic dicarboxylic acid is preferable. There is no restriction | limiting in particular as said C8-C20 aromatic dicarboxylic acid, According to the objective, it can select suitably, For example, a phthalic acid, isophthalic acid, a terephthalic acid, naphthalene dicarboxylic acid etc. are mentioned. In particular, in order to impart a property of low Tg and easy deformation at low temperatures, it is preferable to contain 50% by mass or more of aliphatic dicarboxylic acid having 4 to 12 carbon atoms in the total dicarboxylic acid component.

-3 or higher acid or alcohol
As a non-linear component, that is, a component for taking a branched structure, a conventionally known trivalent or higher alcohol can be used.
Examples of alcohols include trihydric or higher aliphatic alcohols, trihydric or higher polyphenols, and alkylene oxide adducts of trihydric or higher polyphenols. The trihydric or higher aliphatic alcohol is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and sorbitol. The trihydric or higher polyphenols are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include trisphenol PA, phenol novolac, and cresol novolak. Examples of the alkylene oxide adducts of trihydric or higher polyphenols include those obtained by adding alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide to trihydric or higher polyphenols.
Examples of the acid include trivalent or higher aromatic carboxylic acids. There is no restriction | limiting in particular as said trivalent or more aromatic carboxylic acid, Although it can select suitably according to the objective, C9-C20 trivalent or more aromatic carboxylic acid is preferable. There is no restriction | limiting in particular as said C9-C20 trivalent or more aromatic carboxylic acid, According to the objective, it can select suitably, For example, trimellitic acid, pyromellitic acid, etc. are mentioned.
As the polycarboxylic acid, an acid anhydride or a lower alkyl ester of any of dicarboxylic acid, trivalent or higher carboxylic acid, and a mixture of dicarboxylic acid and trivalent or higher carboxylic acid may be used. There is no restriction | limiting in particular as said lower alkyl ester, According to the objective, it can select suitably, For example, methyl ester, ethyl ester, isopropyl ester, etc. are mentioned.

-Isocyanate-
As the component of the isocyanate, an aromatic diisocyanate having 6 to 20 carbon atoms (excluding carbon in the NCO group, the same shall apply hereinafter), an aliphatic diisocyanate having 2 to 18 carbon atoms, an alicyclic diisocyanate having 4 to 15 carbon atoms, C8-15 aromatic diisocyanates and modified products of these diisocyanates (urethane groups, carbodiimide groups, allophanate groups, urea groups, burette groups, uretdione groups, uretoimine groups, isocyanurate groups, oxazolidone group-containing modified products, etc. And mixtures of two or more thereof.
Moreover, you may use together polyisocyanate more than trivalence as needed.

Specific examples of the aromatic diisocyanate (including triisocyanate or higher polyisocyanate) include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI). ), Crude TDI, 2,4′- and / or 4,4′-diphenylmethane diisocyanate (MDI), crude MDI [crude diaminophenylmethane [condensation product of formaldehyde with an aromatic amine (aniline) or a mixture thereof; A mixture of diphenylmethane and a small amount (for example, 5 to 20% by mass) of a trifunctional or higher polyamine] Phosgenation compound: polyallyl polyisocyanate (PAPI)], 1,5-naphthylene diisocyanate, 4,4 ′, 4 ″ -Triphenylmethane triisocyanate, m- and p-isocyanatopheny Such as sulfonyl isocyanate.
Specific examples of the aliphatic diisocyanate (including triisocyanate or higher polyisocyanate) include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2, 2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2 , 6-diisocyanatohexanoate and the like.
Specific examples of the alicyclic diisocyanate include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2- And isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5- and / or 2,6-norbornane diisocyanate.
Specific examples of the aromatic aliphatic diisocyanate include m- and / or p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI), and the like.

Examples of the modified diisocyanate include urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, and oxazolidone group-containing modified product.
Specifically, modified MDI (urethane modified MDI, carbodiimide modified MDI, trihydrocarbyl phosphate modified MDI, etc.), modified products of diisocyanates such as urethane modified TDI, and mixtures of two or more thereof [for example, modified MDI and urethane modified TDI (Combined use with an isocyanate-containing prepolymer)] is included.
Among these, preferred are aromatic diisocyanates having 6 to 15 carbon atoms, aliphatic diisocyanates having 4 to 12 carbon atoms, and alicyclic diisocyanates having 4 to 15 carbon atoms, and particularly preferred are TDI, MDI and HDI. , Hydrogenated MDI, and IPDI.

As the curing agent that reacts with isocyanate, a conventionally known amine compound can be suitably used.
Examples of diamines (including triamine or higher polyamines used as necessary) include aliphatic diamines (C2 to C18): [1] aliphatic diamines (C2 to C6 alkylenediamines (ethylenediamine, propylenediamine, trimethylene) Diamine, tetramethylenediamine, hexamethylenediamine, etc.), polyalkylene (C2-C6) diamine (diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.)) [2] These alkyl (C1 to C4) or hydroxyalkyl (C2 to C4) substitutes [dialkyl (C1 to C3) aminopropylamine, trimethylhexamethylenediamine, aminoethylethanol; Min, 2,5-dimethyl-2,5-hexamethylenediamine, methyliminobispropylamine, etc.]; [3] Alicyclic or heterocyclic-containing aliphatic diamines (alicyclic diamines (C4 to C15) [1,3 -Diaminocyclohexane, isophoronediamine, mensendiamine, 4,4'-methylenedicyclohexanediamine (hydrogenated methylenedianiline), etc.], heterocyclic diamine (C4-C15) [piperazine, N-aminoethylpiperazine, 1, 4-diaminoethylpiperazine, 1,4bis (2-amino-2-methylpropyl) piperazine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] [4] Aromatic ring-containing aliphatic amines (C8-C15) (xylylenediamine, tetrachloro-p-ki) Rirenjiamin, etc.), and the like.

As aromatic diamines (C6-C20),
[1]: unsubstituted aromatic diamine [1,2-, 1,3- and 1,4-phenylenediamine, 2,4′- and 4,4′-diphenylmethanediamine, crude diphenylmethanediamine (polyphenylpolymethylenepolyamine ), Diaminodiphenylsulfone, benzidine, thiodianiline, bis (3,4-diaminophenyl) sulfone, 2,6-diaminopyridine, m-aminobenzylamine, triphenylmethane-4,4 ′, 4 ″ -triamine, naphthylene Amines;
[2]: Aromatic diamine having a nucleus-substituted alkyl group [C1-C4 alkyl group such as methyl, ethyl, n- and i-propyl, butyl], for example, 2,4- and 2,6-tolylenediamine, crude Tolylenediamine, diethyltolylenediamine, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 4,4′-bis (o-toluidine), dianisidine, diaminoditolylsulfone, 1,3-dimethyl-2 , 4-diaminobenzene, 1,3-dimethyl-2,6-diaminobenzene, 1,4-diisopropyl-2,5-diaminobenzene, 2,4-diaminomesitylene, 1-methyl-3,5-diethyl-2 , 4-diaminobenzene, 2,3-dimethyl-1,4-diaminonaphthalene, 2,6-dimethyl-1,5-diaminonaphthalene, 3,3 ′ , 5,5′-tetramethylbenzidine, 3,3 ′, 5,5′-tetramethyl-4,4′-diaminodiphenylmethane, 3,5-diethyl-3′-methyl-2 ′, 4-diaminodiphenylmethane, 3,3′-diethyl-2,2′-diaminodiphenylmethane, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 3,3 ′, 5,5′-tetraethyl-4,4′-diaminobenzophenone, 3,3 ′, 5,5′-tetraethyl-4,4′-diaminodiphenyl ether, 3,3 ′, 5,5′-tetraisopropyl-4,4′-diaminodiphenylsulfone, and the like, and isomers thereof Various proportions of mixtures;
[3]: Aromatic diamine having a nucleus-substituted electron withdrawing group (halogen such as Cl, Br, I, F; nitro group, etc.) or an alkoxy group such as methoxy and ethoxy [methylenebis-o-chloroaniline, 4-chloro- o-phenylenediamine, 2-chloro-1,4-phenylenediamine, 3-amino-4-chloroaniline, 4-bromo-1,3-phenylenediamine, 2,5-dichloro-1,4-phenylenediamine, 5 -Nitro-1,3-phenylenediamine, 3-dimethoxy-4-aminoaniline; 4,4'-diamino-3,3'-dimethyl-5,5'-dibromo-diphenylmethane, 3,3'-dichlorobenzidine, 3,3′-dimethoxybenzidine, bis (4-amino-3-chlorophenyl) oxide, bis (4-amino-2-chlorophenyl) pro Bis (4-amino-2-chlorophenyl) sulfone, bis (4-amino-3-methoxyphenyl) decane, bis (4-aminophenyl) sulfide, bis (4-aminophenyl) telluride, bis (4-amino) Phenyl) selenide, bis (4-amino-3-methoxyphenyl) disulfide, 4,4′-methylenebis (2-iodoaniline), 4,4′-methylenebis (2-bromoaniline), 4,4′-methylenebis ( 2-fluoroaniline), 4-aminophenyl-2-chloroaniline and the like];
[4]: Aromatic diamine having a secondary amino group [a part or all of —NH 2 of the aromatic diamine of the above [1] to [3] is —NH—R ′ (R ′ is an alkyl group such as methyl, ethyl Etc.] [4,4′-di (methylamino) diphenylmethane, 1-methyl-2-methylamino-4-aminobenzene, etc.].
In addition to these, the diamine component can be obtained by condensation of polyamide polyamine [dicarboxylic acid (dimer acid etc.) and excess (more than 2 mol per mole of acid) polyamine (alkylenediamine, polyalkylenepolyamine etc.). Low molecular weight polyamide polyamine, etc.], polyether polyamine [hydride of cyanoethylated polyether polyol (polyalkylene glycol, etc.), etc.].

  The weight average molecular weight of the amorphous polyester resin A is preferably 20,000 or more and less than 1,000,000. The average molecular weight of the amorphous polyester resin A is the molecular weight of the reaction product obtained by reacting the reactive precursor and the curing agent. When the weight average molecular weight is 20,000 or more, it is possible to prevent the problem that the toner easily flows at a low temperature and is inferior in heat resistant storage stability. Moreover, the problem that the viscosity at the time of melting becomes low and the high temperature offset property is poor can be prevented.

<< Amorphous polyester resin B, C >>
The amorphous polyester resins B and C are preferably linear polyester resins. The polyester resin is obtained using a diol component and a dicarboxylic acid. In particular, the amorphous polyester resin B includes a unit obtained from any one of the sulfo-substituted benzene dicarboxylic acid metal salt and the ester thereof, and contributes to pigment dispersibility and modification.

  Examples of the diol component include polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane and polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl). Alkylene (2 to 3 carbon atoms) oxide (average number of added moles 1 to 10) adduct of bisphenol A such as propane; ethylene glycol, propylene glycol, hydrogenated bisphenol A, or alkylene (2 to 3 carbon atoms) oxide thereof (Average addition mole number 1-10) Adduct etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.

The amorphous polyester resin B containing a unit obtained from any one of the sulfo-substituted benzene dicarboxylic acid metal salt and an ester thereof (hereinafter abbreviated as sulfo-substituted benzene dicarboxylic acid metal salt) is the sulfo-substituted benzene dicarboxylic acid. It can be obtained by copolymerizing acid metal salts with other dicarboxylic acid components and diol components.
Examples of the sulfo-substituted benzenedicarboxylic acid metal salts include lithium sulfophthalate, sodium sulfophthalate, potassium sulfophthalate, rubidium sulfophthalate, cesium sulfophthalate, lithium sulfoisophthalate, sodium sulfoisophthalate, potassium sulfoisophthalate, rubidium sulfoisophthalate. Cesium sulfoisophthalate, lithium sulfoterephthalate, sodium sulfoterephthalate, potassium sulfoterephthalate, rubidium sulfoterephthalate, cesium sulfoterephthalate, and alkyl esters thereof. These may be used individually by 1 type and may use 2 or more types together. Of these, sodium salts are preferable, and sodium 5-sulfoisophthalate is particularly preferable.

  The content of the sulfo-substituted benzenedicarboxylic acid metal salt as an acid monomer constituting the polyester resin in the toner is preferably 0.1% by mass or more and less than 1% by mass. If it is 0.1% by mass or more, it is effective for pigment dispersibility and deforming, and if it is less than 1% by mass, it is possible to prevent the problem that the viscosity becomes high and the toner fixing characteristics deteriorate. Means for adjusting the content of the sulfo-substituted benzenedicarboxylic acid metal salt in the toner include the content of the sulfoisophthalic acid metal salt in the amorphous polyester resin B or the toner of the amorphous polyester resin B in the toner. What is necessary is just to adjust content.

  Among the dicarboxylic acid components, the components other than the sulfo-substituted benzene dicarboxylic acid metal salts include, for example, dicarboxylic acids such as adipic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, maleic acid; dodecenyl succinic acid, octyl succinic acid, etc. And succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms. These may be used individually by 1 type and may use 2 or more types together.

  In the present invention, for the purpose of adjusting the acid value and the hydroxyl value, tricarboxylic acid such as trimellitic acid, pyromellitic acid or anhydride of these acids, glycerin, pentaerythritol, trimethylolpropane at the end of the resin chain. Such trivalent or higher polyols may be included.

The molecular weights of the amorphous polyester resins B and C are not particularly limited and may be appropriately selected depending on the intended purpose. However, if the molecular weight is too low, the heat resistant storage stability of the toner, stirring in the developing device When the molecular weight is too high, the viscoelasticity at the time of melting of the toner may be high and the low-temperature fixability may be poor. It is preferable that they are 1,000-10,000, number average molecular weight (Mn) 1,000-4,000, and Mw / Mn 1.0-4.0.
Furthermore, it is preferable that they are weight average molecular weight (Mw) 4,000-7,000, number average molecular weight (Mn) 1,500-3,000, and Mw / Mn 1.0-3.5.

The acid value of the amorphous polyester resins B and C is not particularly limited and may be appropriately selected depending on the intended purpose. g is more preferable.
When the acid value is 1 mgKOH / g or more, the toner is likely to be negatively charged, and further, the affinity between the paper and the toner is improved when fixing to paper, and the low-temperature fixability can be improved. .
When the acid value is 50 mgKOH / g or less, it is possible to prevent a decrease in charging stability, particularly charging stability against environmental fluctuation.
There is no restriction | limiting in particular as the hydroxyl value of the said amorphous polyester resin B and C, Although it can select suitably according to the objective, It is preferable that it is 5 mgKOH / g or more.

  The glass transition temperature (Tg) of the amorphous polyester resins B and C is preferably 40 ° C. or higher and lower than 70 ° C. When the Tg of the polyester resin that is linear and does not have a crosslinked structure is too low, the toner has poor heat resistance and durability against stress such as stirring in the developing device, and when the Tg is too high, the toner is fixed. This is because the deformation due to heating and pressurization is insufficient and the low-temperature fixability is poor.

  The total content of the amorphous polyester resins B and C in the toner may be 50% by mass or more and 80% by mass or less.

The molecular structures of the amorphous polyester resins B and C include X-ray diffraction, gas chromatograph mass spectrometry (GC / MS), liquid chromatograph mass spectrometry (NMR) measurement in addition to nuclear magnetic resonance spectroscopy (NMR) measurement using solutions and solids. LC / MS), infrared spectroscopy (IR) measurement and the like.
Conveniently, the resin is dissolved in a mixed solvent of trifluoroacetic acid / deuterated chloroform = 1/1, then a nuclear magnetic resonance spectrum (1H-NMR) is measured, and the molecular structure is confirmed from the spectrum pattern according to a conventional method. Etc.

<< Crystalline polyester resin >>
Since the crystalline polyester resin has high crystallinity, it exhibits a heat-melting characteristic that exhibits a sudden viscosity drop near the fixing start temperature. By using the crystalline polyester resin having such characteristics together with the amorphous polyester resin, the heat resistant storage stability due to the crystallinity is good until just before the melting start temperature, and at the melting start temperature, the rapid melting due to the melting of the crystalline polyester. A toner that has good heat-resistant storage stability and low-temperature fixability because it causes a viscosity drop (sharp melt property) and is compatible with the amorphous polyester resin, and the viscosity is rapidly reduced together. can get. Also, good results are shown for the release width (difference between the fixing lower limit temperature and the hot offset occurrence temperature).
The crystalline polyester resin is obtained using a polyhydric alcohol component and a polyvalent carboxylic acid component such as a polyvalent carboxylic acid, a polyvalent carboxylic acid anhydride, or a polyvalent carboxylic acid ester.
In the present invention, the crystalline polyester resin, as described above, uses a polyhydric alcohol component and a polyvalent carboxylic acid component such as a polyvalent carboxylic acid, a polyvalent carboxylic acid anhydride, or a polyvalent carboxylic acid ester. What obtained is a modified polyester resin does not belong to the crystalline polyester resin.

-Polyhydric alcohol component-
There is no restriction | limiting in particular as said polyhydric alcohol component, According to the objective, it can select suitably, For example, diol and trihydric or more alcohol are mentioned.
Examples of the diol include saturated aliphatic diol. Examples of the saturated aliphatic diol include linear saturated aliphatic diols and branched saturated aliphatic diols. Among these, linear saturated aliphatic diols are preferable, and straight chain having 4 to 12 carbon atoms. A chain saturated aliphatic diol is more preferred. When the saturated aliphatic diol is branched, the crystallinity of the crystalline polyester resin may be lowered, and the melting point may be lowered. Further, when the main chain portion has 4 or more carbon atoms, it is possible to prevent a problem that when the polycondensation with the aromatic dicarboxylic acid is carried out, the melting temperature becomes high and the low-temperature fixing becomes difficult. On the other hand, when the number of carbon atoms is 12 or less, it is easy to obtain materials, which is practically preferable. The number of carbon atoms is more preferably 12 or less.
Examples of the saturated aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1, 8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1, Examples thereof include 18-octadecanediol and 1,14-eicosandecanediol. Among these, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol is the point that the crystalline polyester resin has high crystallinity and excellent sharp melt properties. 1,12-dodecanediol is preferred.
Examples of the trihydric or higher alcohol include glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol.
These may be used individually by 1 type and may use 2 or more types together.

-Polycarboxylic acid component-
There is no restriction | limiting in particular as said polyvalent carboxylic acid component, According to the objective, it can select suitably, For example, bivalent carboxylic acid and trivalent or more carboxylic acid are mentioned.
Examples of the divalent carboxylic acid include oxalic acid, succinic acid, glutaric acid, adipic acid, peric acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1, Saturated aliphatic dicarboxylic acids such as 12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid; phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, malonic acid, Aromatic dicarboxylic acids such as dibasic acids such as mesaconic acid; and the like, and anhydrides and lower alkyl esters thereof.
Examples of the trivalent or higher carboxylic acid include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, and the like, and anhydrides thereof. And the lower alkyl esters.
In addition to the saturated aliphatic dicarboxylic acid and aromatic dicarboxylic acid, the polyvalent carboxylic acid component may include a dicarboxylic acid component having a sulfonic acid group. Further, in addition to the saturated aliphatic dicarboxylic acid and aromatic dicarboxylic acid, a dicarboxylic acid component having a double bond may be contained.
These may be used individually by 1 type and may use 2 or more types together.

  The crystalline polyester resin includes a structural unit derived from a saturated aliphatic dicarboxylic acid having 4 to 12 carbon atoms and a structural unit derived from a saturated aliphatic diol having 2 to 12 carbon atoms. It is preferable in that it can exhibit excellent low-temperature fixability because of its high properties and excellent sharp melt properties.

  There is no restriction | limiting in particular as melting | fusing point of the said crystalline polyester resin, Although it can select suitably according to the objective, It is preferable that it is 60 to 80 degreeC. When the melting point is 60 ° C. or higher, the crystalline polyester resin is difficult to melt at a low temperature, and the heat resistant storage stability of the toner can be prevented from being lowered. The polyester resin can be sufficiently melted to prevent the low-temperature fixability from being lowered.

The molecular weight of the crystalline polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose. However, those having a sharp molecular weight distribution and a low molecular weight are excellent in low-temperature fixability, and many components have a low molecular weight. From the viewpoint that heat-resistant storage stability deteriorates, the soluble content of orthodichlorobenzene in the crystalline polyester resin is determined by GPC measurement to have a weight average molecular weight (Mw) of 3,000 to 30,000 and a number average molecular weight (Mn). It is preferably 1,000 to 10,000 and Mw / Mn 1.0 to 10.
Furthermore, it is preferable that they are weight average molecular weight (Mw) 5,000-15,000, number average molecular weight (Mn) 2,000-10,000, and Mw / Mn 1.0-5.0.

The acid value of the crystalline polyester resin is not particularly limited and can be appropriately selected according to the purpose. From the viewpoint of the affinity between paper and resin, in order to achieve desired low-temperature fixability, 5 mgKOH / g or more is preferable and 10 mgKOH / g or more is more preferable. On the other hand, in order to improve the high temperature offset resistance, 45 mgKOH / g or less is preferable.
The hydroxyl value of the crystalline polyester resin is not particularly limited and may be appropriately selected according to the purpose. However, in order to achieve a desired temperature fixability and good charging characteristics, 0 mgKOH / G to 50 mgKOH / g are preferable, and 5 mgKOH / g to 50 mgKOH / g are more preferable.

The molecular structure of the crystalline polyester resin can be confirmed by X-ray diffraction, GC / MS, LC / MS, IR measurement, etc. in addition to NMR measurement by solution or solid. As a simple method, there is a method of detecting, as a crystalline polyester resin, an infrared absorption spectrum having an absorption based on δCH (out-of-plane variable vibration) of olefin at 965 ± 10 cm ⁻¹ or 990 ± 10 cm ⁻¹ .

  There is no restriction | limiting in particular as content of the said crystalline polyester resin, Although it can select suitably according to the objective, 2 mass parts-20 mass parts are preferable with respect to 100 mass parts of said toners, 5 mass parts -15 mass parts is more preferable. When the content is 2 parts by mass or more, sharp melting with a crystalline polyester resin is sufficient and low temperature fixability can be prevented from being deteriorated. When the content is 20 parts by mass or less, heat resistant storage stability is deteriorated. And image fogging can be prevented. When the content is in the more preferable range, it is advantageous in that it is excellent in all of high image quality, high stability, and low-temperature fixability.

<Release agent>
There is no restriction | limiting in particular as said mold release agent, It can select suitably from well-known things.
Examples of mold release agents for waxes and waxes include plant waxes such as carnauba wax, cotton wax, wood wax, and rice wax; animal waxes such as beeswax and lanolin; mineral waxes such as ozokerite and cercin; And natural waxes such as petroleum waxes such as paraffin, microcrystalline, and petrolatum.
In addition to these natural waxes, synthetic hydrocarbon waxes such as Fischer-Tropsch wax, polyethylene, and polypropylene; synthetic waxes such as esters, ketones, and ethers;
Furthermore, fatty acid amide compounds such as 12-hydroxystearic acid amide, stearic acid amide, phthalic anhydride imide, and chlorinated hydrocarbons; low molecular weight crystalline polymer resin, poly-n-stearyl methacrylate, poly-n -Polyacrylate homopolymer or copolymer such as lauryl methacrylate (eg, n-stearyl acrylate-ethyl methacrylate copolymer); crystalline polymer having a long alkyl group in the side chain, etc. Good.
Among these, hydrocarbon waxes such as paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyethylene wax, and polypropylene wax are preferable.

  The melting point of the release agent can be appropriately selected according to the purpose, but is preferably 50 ° C. or higher and lower than 90 ° C., more preferably 60 ° C. or higher and lower than 80 ° C. When the temperature is 50 ° C. or higher, it is possible to prevent the problem that the release agent is easily melted at low temperatures and the heat resistant storage stability is poor. When the temperature is lower than 90 ° C., it is possible to prevent a problem that the release agent is not sufficiently melted and a fixing offset is generated and an image is lost when the binder resin of the present invention is in the fixing temperature region. it can.

  There is no restriction | limiting in particular as content of the said mold release agent, Although it can select suitably according to the objective, 2 mass parts-10 mass parts are preferable with respect to 100 mass parts of said toner, 3 mass parts- 8 parts by mass is more preferable. When the content is 2 parts by mass or more, the problem of poor high temperature offset resistance and low temperature fixability at the time of fixing can be prevented, and when the content is 10 parts by mass or less, heat resistant storage stability is deteriorated and image fogging is caused. It is possible to prevent the problem that occurs. When the content is in the more preferable range, it is advantageous in terms of improving the image quality and improving the fixing stability.

<Colorant>
There is no restriction | limiting in particular as said coloring agent, According to the objective, it can select suitably, For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow , Yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Lead Red, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Faisa Red, Lachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Tolujing Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oil Red, Quinacridone , Pyrazolone red, polyazo red, chrome vermilion, benzidine orange, perinone orange, oil orange, cobalt blue, cerulean blue, alkali blue rake, peacock blue rake, Victoria blue rake, metal free phthalocyanine blue, phthalocyanine blue, fast sky blue, Indanthrene blue (RS, BC), indigo, ultramarine blue, bitumen, anthraquinone blue, fast violet B, methyl violet lake, cobalt purple, manganese purple, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Examples include green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, and ritbon.

  There is no restriction | limiting in particular as content of the said coloring agent, Although it can select suitably according to the objective, 1 mass part-15 mass parts are preferable with respect to 100 mass parts of said toners, and 3 mass parts-10 parts. Part by mass is more preferable.

The colorant can also be used as a master batch combined with a resin. Examples of the resin to be kneaded together with the production of the master batch or the master batch include, in addition to the amorphous polyester resin, a polymer of styrene such as polystyrene, poly p-chlorostyrene, polyvinyl toluene, or a substituted product thereof; styrene-p -Chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene- Butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethacrylic acid Methyl copolymer, styrene-acrylo Tolyl copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester Styrene copolymers such as copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid Resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, and the like. These may be used singly or Combine two or more types However, it is preferable to use the amorphous polyester resin C.
The masterbatch can be obtained by mixing a masterbatch resin and a colorant under high shearing force and kneading to obtain a masterbatch. In this case, an organic solvent can be used in order to enhance the interaction between the colorant and the resin. In addition, a so-called flushing method, which is a wet method of colorant, is a method of mixing and kneading an aqueous paste containing water of a colorant together with a resin and an organic solvent, transferring the colorant to the resin side, and removing moisture and organic solvent components. Since the cake can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

<Other ingredients>
<< Charge Control Agent >>
The charge control agent is not particularly limited and may be appropriately selected depending on the intended purpose.For example, nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, Alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine activators, salicylic acid metal salts, metal salts of salicylic acid derivatives, etc. It is. Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of phenol-based condensate (above, manufactured by Orient Chemical Co., Ltd.), TP-302, TP-415 of quaternary ammonium salt molybdenum complex (above, manufactured by Hodogaya Chemical Co., Ltd.), LRA- 901, boron complex LR-147 (manufactured by Nippon Carlit Co., Ltd.), copper phthalocyanine, perylene, quinacridone, azo pigment, other polymer compounds having functional groups such as sulfonic acid group, carboxyl group, quaternary ammonium salt Is mentioned.
The content of the charge control agent is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.1 parts by mass to 10 parts by mass with respect to 100 parts by mass of the toner. 2 mass parts-5 mass parts are more preferable. When the content is 10 parts by mass or less, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic attraction force with the developing roller is increased, and the fluidity of the developer is lowered. In addition, various problems such as a decrease in image density can be prevented. These charge control agents can be dissolved and dispersed after being melt-kneaded with a masterbatch and resin, or of course, may be added when directly dissolving or dispersing in an organic solvent, or may be fixed on the toner surface after preparation of toner particles. May be.

<< External additive >>
As the external additive, in addition to oxide fine particles, inorganic fine particles or hydrophobic treated inorganic fine particles can be used in combination. The volume average particle size of the hydrophobized primary particles is preferably 1 nm to 100 nm, preferably 5 nm to A 70 nm inorganic fine particle is more preferable.
Moreover, it is preferable that at least one kind of inorganic fine particles having a volume average particle diameter of 20 nm or less of the hydrophobized primary particles and at least one kind of inorganic fine particles of 30 nm or more are contained. In addition, the specific surface area by BET method ^is preferably 20m ² / g~500m 2 / g.
The external additive is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include silica fine particles, hydrophobic silica, fatty acid metal salts (for example, zinc stearate and aluminum stearate), and metal oxides. (For example, titania, alumina, tin oxide, antimony oxide, etc.), fluoropolymer, and the like.
Suitable additives include hydrophobized silica, titania, titanium oxide, and alumina fine particles. Examples of the silica fine particles include R972, R974, RX200, RY200, R202, R805, and R812 (all manufactured by Nippon Aerosil Co., Ltd.). Moreover, as titania fine particles, for example, P-25 (manufactured by Nippon Aerosil Co., Ltd.), STT-30, STT-65C-S (both manufactured by Titanium Industry Co., Ltd.), TAF-140 (manufactured by Fuji Titanium Industry Co., Ltd.), MT-150W, MT-500B, MT-600B, MT-150A (all of which are manufactured by Teika Corporation), and the like.
Examples of the hydrophobized titanium oxide fine particles include T-805 (manufactured by Nippon Aerosil Co., Ltd.), STT-30A, STT-65S-S (all manufactured by Titanium Industry Co., Ltd.), TAF-500T, and TAF-1500T. (Both manufactured by Fuji Titanium Industry Co., Ltd.), MT-100S, MT-100T (all manufactured by Teika Co., Ltd.), IT-S (manufactured by Ishihara Sangyo Co., Ltd.), and the like.
In order to obtain hydrophobized oxide microparticles, hydrophobized silica microparticles, hydrophobized titania microparticles, and hydrophobized alumina microparticles, hydrophilic microparticles can be obtained using methyltrimethoxysilane or methyltrimethylsilane. It can be obtained by treating with a silane coupling agent such as ethoxysilane or octyltrimethoxysilane. In addition, silicone oil-treated oxide fine particles and inorganic fine particles obtained by treating silicone oil with heat if necessary to treat it with inorganic fine particles are also suitable.
Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, chlorophenyl silicone oil, methyl hydrogen silicone oil, alkyl-modified silicone oil, fluorine-modified silicone oil, polyether-modified silicone oil, alcohol-modified silicone oil, amino-modified. Silicone oil, epoxy-modified silicone oil, epoxy-polyether-modified silicone oil, phenol-modified silicone oil, carboxyl-modified silicone oil, mercapto-modified silicone oil, acrylic, methacryl-modified silicone oil, α-methylstyrene-modified silicone oil, and the like can be used. Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, iron oxide, copper oxide, zinc oxide, tin oxide, quartz sand, clay, mica, and silica ash. Examples thereof include stone, diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, parium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. Among these, silica and titanium dioxide are particularly preferable.
There is no restriction | limiting in particular as content of the said external additive, Although it can select suitably according to the objective, 0.1 mass%-5 mass% are preferable with respect to the said toner, 0.3 mass%-3 The mass% is more preferable.
There is no restriction | limiting in particular as a volume average particle diameter of the primary particle of the said inorganic fine particle, Although it can select suitably according to the objective, 100 nm or less is preferable and 3 nm or more and 70 nm or less are more preferable. If it is 3 nm or more, it is possible to prevent the problem that the inorganic fine particles are buried in the toner and the function is not effectively exhibited. Further, when the thickness is 100 nm or less, it is possible to prevent the problem that the surface of the photoreceptor is damaged unevenly.

<< Flowability improver >>
The fluidity improver is not particularly limited as long as it is surface-treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity, and is appropriately selected according to the purpose. For example, silane coupling agents, silylating agents, silane coupling agents having a fluorinated alkyl group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils, etc. Can be mentioned. It is particularly preferable that the silica and the titanium oxide are surface-treated with such a fluidity improver and used as hydrophobic silica and hydrophobic titanium oxide.

<< Cleaning improver >>
The cleaning property improving agent is not particularly limited as long as it is added to the toner in order to remove the developer after transfer remaining on the photosensitive member or the primary transfer medium, and is appropriately selected according to the purpose. Examples thereof include fatty acid metal salts such as zinc stearate, calcium stearate and stearic acid, polymer fine particles produced by soap-free emulsion polymerization such as polymethyl methacrylate fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution, and those having a volume average particle size of 0.01 μm to 1 μm are suitable.

<< Magnetic material >>
There is no restriction | limiting in particular as said magnetic material, According to the objective, it can select suitably, For example, iron powder, magnetite, a ferrite, etc. are mentioned. Among these, white is preferable in terms of color tone.

<Toner characteristics>
<< Average circularity >>
The average circularity of the toner is 0.940 to 0.970.
Here, the average circularity is a value obtained by dividing the circumference of an equivalent circle having the same projected area as the shape of the toner by the circumference of the actual particle.
The average circularity is preferably 0.940 to 0.970, and more preferably 0.940 to 0.955. The particles having an average circularity of less than 0.940 are preferably 15% or less.
When the average circularity is 0.940 or more, a high-quality image with good transferability and no dust is obtained, and when it is 0.970 or less, in an image forming system employing blade cleaning or the like, In the case of forming an image with a high image area ratio such as a photographic image such as a defective cleaning on the photosensitive member or the transfer belt, or a stain on the image, for example, a toner that forms an untransferred image due to a defective feeding or the like It is possible to effectively prevent problems such as the occurrence of smudges on images accumulated as transfer residual toner on the body. In addition, it is possible to effectively prevent a problem that the charging roller for contacting and charging the photosensitive member is contaminated and the original charging ability cannot be exhibited.

<< Average particle diameter of toner >>
The volume average particle diameter of the toner is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is preferably 3 μm or more and 8 μm or less.
When the volume average particle size is 3 μm or more, the two-component developer can prevent the problem that the toner is fused to the surface of the carrier during a long period of stirring in the developing device and the charging ability of the carrier is lowered. Further, in the case of a one-component developer, filming of toner on the developing roller and thinning of the toner make it possible to prevent problems that the toner is likely to be fused to a member such as a blade, which is 8 μm or less. Thus, high-resolution and high-quality images can be easily obtained, and fluctuations in the toner particle diameter can be suppressed when the balance of the toner in the developer is performed.
The ratio of the volume average particle diameter (Dv) to the number average particle diameter (Dn) in the toner (volume average particle diameter / number average particle diameter) is preferably 1.00 or more and 1.25 or less, and 1.10 or more. 1.25 or less is more preferable.
When the ratio of the volume average particle diameter to the number average particle diameter (Dv / Dn) is 1.25 or less, in the two-component developer, the toner is fused to the surface of the carrier during a long period of stirring in the developing device. Thus, the problem that the charging ability of the carrier is lowered can be prevented. In addition, with the one-component developer, it is possible to prevent problems such as toner filming on the developing roller and toner thinning, which easily causes toner fusion to a member such as a blade. In addition, a high-resolution and high-quality image can be obtained, and fluctuations in the toner particle diameter can be suppressed when the balance of the toner in the developer is performed.

<< Glass Transition Temperature (Tg) >>
As the glass transition temperature (Tg) of the toner, the glass transition temperature (Tg1st) calculated at the first temperature increase in DSC measurement is preferably 18 ° C. or more and less than 40 ° C. If the Tg of conventional toner is about 50 ° C. or lower, toner aggregation is likely to occur due to temperature changes in the storage environment during toner transportation in the summer, and solidification in the toner bottle occurs in the developing machine. Toner sticking occurs, and replenishment failure due to toner clogging in the toner bottle, and more than an image due to toner sticking in the developing machine are likely to occur.
In the toner of the present invention, although the Tg of the toner is lower than before, the low Tg component has a cross-linked structure and has a highly cohesive urethane or urea group, so that heat resistant storage stability can be maintained.
When the Tg1st is 18 ° C. or higher, blocking in the developing machine and filming on the photoreceptor can be prevented even when the resin of the present invention is used. When the temperature is lower than 40 ° C., it is possible to prevent a decrease in low-temperature fixability of the toner.
The difference between the glass transition temperature (Tg2nd) and Tg1st (Tg1st−Tg2nd) calculated at the second temperature increase in the DSC measurement of the toner is preferably 10 ° C. or more. In this case, the crystalline polyester resin and the amorphous polyester resin are incompatible with each other before heating, and the compatibility between the crystalline polyester resin and the amorphous polyester resin proceeds after the heating. For this reason, it is excellent in low temperature fixability.

<Calculation method and analysis method of various characteristics of toner and toner component>
The amorphous polyester resin, the crystalline polyester resin, the Tg, the melting point, the acid value, the hydroxyl value, the molecular weight, etc. of the release agent may be measured as toner raw materials. The separation may be performed by permeation chromatography (GPC) or the like, and the separated components may be calculated by using an analysis method described later.
Separation of each component by GPC can be performed, for example, by the following method.
In GPC measurement using THF (tetrahydrofuran) as a mobile phase, the eluate is fractionated by a fraction collector or the like, and fractions corresponding to a desired molecular weight portion of the entire surface of the elution curve are collected.
After concentrating and drying the collected eluate with an evaporator, etc., the solid content is dissolved in a heavy solvent such as deuterated chloroform or deuterated THF, and ¹ H-NMR measurement is performed. The constituent monomer ratio of can be calculated.
Another method is to calculate the constituent monomer ratio by concentrating the eluate, hydrolyzing with sodium hydroxide, etc., and performing qualitative quantitative analysis of the decomposition products using high performance liquid chromatography (HPLC). Can do.

<< Toner component separation means >>
An example of the separation means for each component when analyzing the toner will be described in detail.
First, 1 g of toner is put into 100 mL of THF, and a solution in which the soluble components are dissolved is obtained while stirring for 30 minutes at 25 ° C.
This is filtered through a membrane filter having an opening of 0.2 μm to obtain a THF soluble component in the toner.
Subsequently, this is melt | dissolved in THF, it is set as the sample for GPC measurement, and it inject | pours into GPC used for the molecular weight measurement of each above-mentioned resin.
On the other hand, a fraction collector is placed at the eluate discharge port of GPC, and the eluate is collected every predetermined count, and the eluate is eluted every 5% in area ratio from the elution curve elution start (curve rise). Get.
Next, for each elution, 30 mg of sample is dissolved in 1 mL of deuterated chloroform, and 0.05% by volume of tetramethylsilane (TMS) is added as a reference substance.
The solution is filled in a 5 mm diameter glass tube for NMR measurement, and a spectrum is obtained by performing integration 128 times at a temperature of 23 ° C. to 25 ° C. using a nuclear magnetic resonance apparatus (JNM-AL400 manufactured by JEOL Ltd.). .
The amorphous polyester resin, the crystalline polyester resin, the monomer composition of the release agent, and the composition ratio contained in the toner can be obtained from the peak integration ratio of the obtained spectrum.
For example, peak assignment is performed as follows, and the component ratio of the constituent monomer is determined from each integral ratio.
The attribution of the peak is, for example,
Near 8.25 ppm: derived from benzene ring of trimellitic acid (for one hydrogen)
8.07 ppm to around 8.10 ppm: derived from benzene ring of terephthalic acid (for 4 hydrogens)
7.1 ppm to 7.25 ppm vicinity: derived from benzene ring of bisphenol A (for 4 hydrogens)
Around 6.8 ppm: derived from benzene ring of bisphenol A (for 4 hydrogens) and from double bond of fumaric acid (for 2 hydrogens)
5.2 ppm to around 5.4 ppm: methine derived from bisphenol A propylene oxide adduct (one hydrogen)
3.7 ppm to around 4.7 ppm: bisphenol A propylene oxide adduct derived from methylene (for 2 hydrogens) and bisphenol A ethylene oxide adduct derived from methylene (for 4 hydrogens)
Around 1.6 ppm: derived from methyl group of bisphenol A (for 6 hydrogens)
It can be.
From these results, for example, the extract recovered in the fraction in which the amorphous polyester resin A accounts for 90% or more can be treated as the resin A.
Similarly, the extract recovered in the fraction in which the amorphous polyester resin B or C accounts for 90% or more is defined as the resin B or C, and the extract recovered in the fraction in which the crystalline polyester resin accounts for 90% or more. As the crystalline polyester resin, the extract recovered in the fraction occupying 90% or more of the release agent can be treated as the release agent.

<< Average circularity >>
The average circularity is measured by, for example, an optical detection band method in which a suspension containing toner particles is passed through an imaging unit detection band on a flat plate, and a particle image is optically detected and analyzed by a CCD camera. For example, it can be measured using a flow type particle image analyzer FPIA-3000 (manufactured by Sysmex Corporation).

<< Measurement of content of sulfo-substituted benzene dicarboxylic acid metal salt >>
As a means for measuring the content of the sulfo-substituted benzenedicarboxylic acid metal salt, for example, 100 mg of a THF soluble portion of a toner is added with 4 mL of dimethyl sulfoxide (DMSO) and 1 mL of a 5N NaOH methanol solution, and stirred at 120 ° C. for 10 minutes. The obtained solution is analyzed by HPLC, and the unit containing the sulfo-substituted benzene dicarboxylic acid metal salt is qualitatively and quantitatively determined from the obtained spectrum to measure the content of the sulfo-substituted benzene dicarboxylic acid metal salt. Examples thereof include a method in which the unit of the sulfo-substituted benzene dicarboxylic acid metal salt in the dissolved component is quantified by LC / MS and the content of the sulfo-substituted benzene dicarboxylic acid metal salt is measured.

<< Measurement Method of Melting Point and Glass Transition Temperature (Tg) >>
The melting point and glass transition temperature (Tg) in the present invention can be measured using, for example, a DSC system (differential scanning calorimeter) (“Q-200”, manufactured by TA Instruments).
Specifically, the melting point and glass transition temperature of the target sample can be measured by the following procedure.
First, about 5.0 mg of a target sample is placed in an aluminum sample container, and the sample container is placed on a holder unit and set in an electric furnace. Subsequently, it heats from -80 degreeC to 150 degreeC with the temperature increase rate of 10 degree-C / min in nitrogen atmosphere. Thereafter, the temperature is decreased from 150 ° C. to −80 ° C. at a temperature decrease rate of 10 ° C./min, and further heated to 150 ° C. at a temperature increase rate of 10 ° C./min, and a differential scanning calorimeter (“Q-200”, TA Instruments The DSC curve is measured using a product manufactured by Ment Corporation.
From the obtained DSC curve, using the analysis program in the Q-200 system, the DSC curve at the first temperature increase can be selected, and the glass transition temperature at the first temperature increase of the target sample can be obtained. Similarly, the DSC curve at the second temperature increase can be selected, and the glass transition temperature of the target sample at the second temperature increase can be obtained.
Further, from the obtained DSC curve, using the analysis program in the Q-200 system, the DSC curve at the first temperature rise is selected, and the endothermic peak top temperature at the first temperature rise of the target sample is obtained as the melting point. Can do. Similarly, the DSC curve at the second temperature increase can be selected, and the endothermic peak top temperature at the second temperature increase of the target sample can be obtained as the melting point.
In the present invention, the glass transition temperature at the first temperature rise when the toner is used as the target sample is Tg1st, and the glass transition temperature at the second temperature rise is Tg2nd.
In addition, regarding the glass transition temperature and melting point of the constituent components such as the amorphous polyester resin, the crystalline polyester resin, and the release agent, unless otherwise specified, the endothermic peak top and Tg at the second temperature rise are The melting point of the target sample, Tg.

<< Measurement Method of Particle Size Distribution >>
The volume average particle diameter (Dv), number average particle diameter (Dn), and ratio (Dv / Dn) of the toner are, for example, Coulter Counter TA-II, Coulter Multisizer II (both manufactured by Coulter, Inc.), etc. Can be measured. In the present invention, Coulter Multisizer II is used. The measurement method is described below.
First, 0.1 mL to 5 mL of a surfactant (preferably polyoxyethylene alkyl ether (nonionic surfactant)) as a dispersant is added to 100 mL to 150 mL of the electrolytic aqueous solution. Here, the electrolytic aqueous solution is a 1 mass% NaCl aqueous solution prepared using primary sodium chloride, and for example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 mg to 20 mg of a measurement sample is further added. The electrolytic aqueous solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the measurement device is used to measure the volume and number of toner particles or toner using a 100 μm aperture as the aperture. Calculate volume distribution and number distribution. From the obtained distribution, the volume average particle diameter (Dv) and the number average particle diameter (Dn) of the toner can be obtained.
As a channel, it is 2.00 micrometers or more and less than 2.52 micrometers; 2.52 micrometers or more and less than 3.17 micrometers; 3.17 micrometers or more and less than 4.00 micrometers; 4.00 micrometers or more and less than 5.04 micrometers; 5.04 micrometers or more and less than 6.35 micrometers; .35 μm or more and less than 8.00 μm; 8.00 μm or more and less than 10.08 μm; 10.08 μm or more and less than 12.70 μm; 12.70 μm or more and less than 16.00 μm; 16.00 μm or more and less than 20.20 μm; Less than 40 μm; 25.40 μm or more and less than 32.00 μm; 3 channels of 32.00 μm or more and less than 40.30 μm are used, and particles having a particle size of 2.00 μm or more and less than 40.30 μm are targeted.

<< Measurement of Molecular Weight of Each Component of Toner >>
The molecular weight of each component of the toner can be measured, for example, by the following method.
Gel permeation chromatography (GPC) measuring device: GPC-8220GPC (manufactured by Tosoh Corporation)
Column: TSKgel SuperHZM-H 15cm triple (made by Tosoh Corporation)
Temperature: 40 ° C
Solvent: tetrahydrofuran (THF)
Flow rate: 0.35 mL / min
Sample: Pretreatment of 0.15% sample injected into 0.4 ml sample: Toner dissolved in tetrahydrofuran THF (Stabilizer-containing Wako Pure Chemicals) at 0.15% by mass and filtered through a 0.2 μm filter, and the filtrate Is used as a sample.
100 μL of the THF sample solution is injected and measured.
In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts.
As standard polystyrene samples for preparing calibration curves, Showdex STANDARD Std.No S-7300, S-210, S-390, S-875, S-1980, S-10.9, S-629, manufactured by Showa Denko KK S-3.0, S-0.580, and toluene are used. An RI (refractive index) detector is used as the detector.

<< Method for measuring hydroxyl value and acid value >>
The hydroxyl value can be measured using a method based on JIS K0070-1966.
The acid value can be measured using a method based on JIS K0070-1992.

<Toner production method>
The method for producing the toner of the present invention is not particularly limited and may be appropriately selected depending on the intended purpose. However, the toner material containing at least a binder resin is dissolved or dispersed in an organic solvent to dissolve or disperse the toner material. Step A for preparing a liquid, Step B for preparing an emulsion or dispersion by adding a solution or dispersion of the toner material in an aqueous medium to emulsify or disperse, and removing the organic solvent from the emulsion or dispersion Thus, the toner particles are preferably produced by the step C of producing toner particles.
More specifically, a solution or dispersion formed by dissolving or dispersing the amorphous polyester resin, the crystalline polyester resin, and a toner material mainly composed of the release agent and the colorant in an organic solvent. The product is emulsified or dispersed in an aqueous medium containing styrene / acrylic resin fine particles and acrylic resin fine particles to prepare an emulsified or dispersed liquid, granulated, and the toner precursor containing the emulsified or dispersed toner material has acrylic resin fine particles. It is preferable to produce a desired toner by removing the organic solvent after depositing and forming toner particles and then heat-treating water containing the toner particles.
More preferably, a solution or dispersion of a toner material containing an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound is emulsified or dispersed in an aqueous medium, and active hydrogen is contained in the aqueous medium. A desired toner is produced by producing toner precursor particles including an adhesive substrate obtained by reacting a group-containing compound and a polymer capable of reacting with an active hydrogen group-containing compound, and attaching acrylic resin fine particles. .

<< Solution or Dispersion of Toner Material >>
The toner material is dissolved or dispersed in a solvent to prepare a toner material dissolved or dispersed liquid. The toner material is not particularly limited as long as the toner can be formed, and can be appropriately selected according to the purpose. For example, the active hydrogen group-containing compound and a polymer (pre-polymer capable of reacting with the active hydrogen group-containing compound) can be selected. Polymer), each of the above polyester resins, a colorant, and a release agent, and may further include the above-described other components such as a charge control agent as necessary. The toner material dissolved or dispersed liquid is preferably prepared by dissolving or dispersing the toner material in an organic solvent. The organic solvent is preferably removed during or after the toner granulation.

-Organic solvent-
The organic solvent that dissolves or disperses the toner material is not particularly limited as long as it is a solvent that can dissolve or disperse the toner material, and can be appropriately selected according to the purpose. Preferred are those having a boiling point of less than 150 ° C. from the viewpoint of ease of removal, for example, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform Monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, and the like can be used. Further, ester solvents are preferable, and ethyl acetate is particularly preferable. These may be used individually by 1 type and may use 2 or more types together. There is no restriction | limiting in particular as the usage-amount of an organic solvent, Although it can select suitably according to the objective, 40-300 mass parts is preferable with respect to 100 mass parts of toner materials, 60-140 mass parts is more preferable, 80 -120 mass parts is more preferable. The toner material is dissolved or dispersed in an organic solvent containing an active hydrogen group-containing compound, a polymer capable of reacting with the active hydrogen group-containing compound, an unmodified polyester resin, a release agent, a colorant, and charge control. The toner material such as an agent can be dissolved or dispersed. In the toner material, components other than the polymer (prepolymer) capable of reacting with the active hydrogen group-containing compound may be added and mixed in the aqueous medium in the preparation of the aqueous medium described later. When the dissolved or dispersed liquid of the toner material is added to the aqueous medium, it may be added to the aqueous medium together with the dissolved or dispersed liquid.

<< Aqueous medium >>
The aqueous medium is not particularly limited and can be appropriately selected from known ones. For example, water, a solvent miscible with water, a mixture thereof, and the like can be used. Is particularly preferred. The solvent miscible with water is not particularly limited as long as it is miscible with water. For example, alcohol, dimethylformamide, tetrahydrofuran, cellosolves, lower ketones, and the like can be used. Examples of the alcohol include methanol, isopropanol, and ethylene glycol. Examples of lower ketones include acetone and methyl ethyl ketone. These may be used individually by 1 type and may use 2 or more types together.
The aqueous medium is prepared, for example, by dispersing styrene / acrylic resin fine particles in an aqueous medium in the presence of an anionic surfactant. The addition amount of the anionic surfactant and the styrene / acrylic resin fine particles in the aqueous medium is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is preferably 0.5 to 10% by mass, respectively. . The acrylic resin fine particles are then added to the aqueous medium. When the acrylic resin fine particles have an aggregating property with the anionic surfactant, it is preferable to disperse the aqueous medium with a high-speed shearing disperser before emulsification.

<< Emulsification or dispersion >>
The dissolution or dispersion of the toner material in the aqueous medium is preferably carried out by dispersing the toner material dissolution or dispersion in the aqueous medium while stirring. There is no restriction | limiting in particular as a dispersion method, According to the objective, it can select suitably, For example, it can carry out using a well-known disperser etc. Examples of the disperser include a low speed shear disperser and a high speed shear disperser. In this toner production method, an adhesive base material is formed when an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound are subjected to an extension reaction or a cross-linking reaction during emulsification or dispersion. The acrylic resin fine particles may be added to the aqueous medium during or after emulsification. It is carried out while dispersing with a high-speed shearing disperser, or after switching to emulsification and switching to low-speed agitation, or appropriately while observing the adhesion of the acrylic resin fine particles to the toner and the immobilization state.

The adhesive base material is an aqueous medium containing an oil phase containing a polymer having reactivity to active hydrogen groups such as a polyester prepolymer having an isocyanate group, together with a compound containing active hydrogen groups such as amines. An aqueous medium in which an oil phase containing a toner material is added in advance with a compound having an active hydrogen group may be produced by emulsifying or dispersing in the aqueous medium and subjecting both to an extension reaction and / or a cross-linking reaction in an aqueous medium. It may be produced by emulsifying or dispersing in an aqueous medium and subjecting both to an extension reaction and / or a crosslinking reaction in an aqueous medium. After the oil phase containing a toner material is emulsified or dispersed in an aqueous medium, You may produce | generate by adding the compound which has a hydrogen group, and carrying out an elongation reaction and / or a crosslinking reaction of both from a particle interface in an aqueous medium. When both are subjected to an extension reaction and / or a crosslinking reaction from the particle interface, a urea-modified polyester resin is preferentially formed on the surface of the toner to be produced, and a concentration gradient of the urea-modified polyester resin can be provided in the toner.
The reaction conditions (reaction time, reaction temperature) for producing the adhesive substrate are not particularly limited, and an active hydrogen group-containing compound, a polymer having a site capable of reacting with the active hydrogen group-containing compound, Depending on the combination, it can be selected as appropriate.
There is no restriction | limiting in particular as said reaction time, Although it can select suitably according to the objective, 10 minutes-40 hours are preferable, and 2 hours-24 hours are more preferable.
There is no restriction | limiting in particular as said reaction temperature, Although it can select suitably according to the objective, 0 to 150 degreeC is preferable and 40 to 98 degreeC is more preferable.

There is no particular limitation on the method for stably forming a dispersion containing a polymer having a site capable of reacting with an active hydrogen group-containing compound such as a polyester prepolymer having an isocyanate group in the aqueous medium. For example, there may be mentioned a method in which an oil phase prepared by dissolving or dispersing a toner material in a solvent is added to an aqueous medium phase and dispersed by shearing force.
The disperser for the dispersion is not particularly limited and can be appropriately selected according to the purpose. For example, a low-speed shear disperser, a high-speed shear disperser, a friction disperser, and a high-pressure jet disperser. And an ultrasonic disperser.
Among these, a high-speed shearing disperser is preferable in that the particle diameter of the dispersion (oil droplets) can be controlled to 2 μm to 20 μm.
When the high-speed shearing disperser is used, conditions such as the number of rotations, the dispersion time, and the dispersion temperature can be appropriately selected according to the purpose.
There is no restriction | limiting in particular as said rotation speed, Although it can select suitably according to the objective, 1,000 rpm-30,000 rpm are preferable, and 5,000 rpm-20,000 rpm are more preferable.
There is no restriction | limiting in particular as said dispersion | distribution time, Although it can select suitably according to the objective, In the case of a batch system, 0.1 minute-5 minutes are preferable.
There is no restriction | limiting in particular as said dispersion | distribution temperature, Although it can select suitably according to the objective, 0 degreeC-150 degreeC is preferable under pressure, and 40 degreeC-98 degreeC is more preferable. In general, dispersion is easier when the dispersion temperature is higher.

The amount of the aqueous medium used when emulsifying or dispersing the toner material is not particularly limited and may be appropriately selected depending on the intended purpose. It is 50 to 2 parts by mass with respect to 100 parts by mass of the toner material. 1,000 parts by mass is preferable, and 100 parts by mass to 1,000 parts by mass is more preferable.
When the amount of the aqueous medium used is 50 parts by mass or more, it is possible to prevent the problem that the dispersed state of the toner material is deteriorated and toner mother particles having a predetermined particle diameter cannot be obtained. A production cost can be suppressed as it is 000 mass parts or less.
When emulsifying or dispersing the oil phase containing the toner material, it is preferable to use a dispersant from the viewpoint of stabilizing the dispersion such as oil droplets to obtain a desired shape and sharpening the particle size distribution. .

There is no restriction | limiting in particular as said dispersing agent, According to the objective, it can select suitably, For example, surfactant, a poorly water-soluble inorganic compound dispersing agent, a polymeric protective colloid, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.
Among these, surfactants are preferable.
The surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, etc. Can be used.
There is no restriction | limiting in particular as said anionic surfactant, According to the objective, it can select suitably, For example, alkylbenzene sulfonate, (alpha) -olefin sulfonate, phosphate ester, etc. are mentioned.
Among these, those having a fluoroalkyl group are preferable.
A catalyst can be used for the elongation reaction and / or the cross-linking reaction in producing the adhesive substrate.
There is no restriction | limiting in particular as said catalyst, According to the objective, it can select suitably, For example, dibutyltin laurate, dioctyltin laurate, etc. are mentioned.

<< Removal of organic solvent >>
The method for removing the organic solvent from the dispersion such as the emulsified slurry is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the temperature of the entire reaction system is gradually raised, Examples thereof include a method of evaporating the organic solvent, a method of spraying the dispersion liquid in a dry atmosphere, and removing the organic solvent in the oil droplets.
When the organic solvent is removed, toner base particles are formed. The toner base particles can be washed, dried, etc., and further classified. The classification may be performed by removing fine particle portions in a liquid by a cyclone, a decanter, centrifugation, or the like, or may be performed after drying.
The obtained toner base particles may be mixed with particles such as the external additive and the charge control agent. At this time, by applying a mechanical impact force, it is possible to prevent the particles such as the external additive from detaching from the surface of the toner base particles.
The method for applying the mechanical impact force is not particularly limited and can be appropriately selected depending on the purpose. For example, a method for applying the impact force to the mixture using blades rotating at high speed, And a method of causing the particles to collide with each other or a suitable collision plate.
The apparatus used in the above method is not particularly limited and can be appropriately selected according to the purpose. For example, an ang mill (manufactured by Hosokawa Micron), an I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) Examples of such devices include a device with a lowered heel, a hybridization system (manufactured by Nara Machinery Co., Ltd.), a kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), and an automatic mortar.

(Developer)
The developer of the present invention contains at least the toner and, if necessary, other components such as a carrier as appropriate.
For this reason, it is excellent in transferability, chargeability, etc., and a high quality image can be formed stably. The developer may be a one-component developer or a two-component developer. However, when used in a high-speed printer or the like that supports an increase in information processing speed in recent years, the lifetime is shortened. A two-component developer is preferred because it improves.
When the developer is used as a one-component developer, even if the balance of the toner is performed, there is little fluctuation in the particle size of the toner, and members such as a filming of the toner on the developing roller and a blade for thinning the toner The toner is less fused to the toner, and good and stable developability and images can be obtained even with long-term stirring in the developing device.
When the developer is used as a two-component developer, even if the toner balance for a long period of time is performed, the fluctuation of the toner particle diameter is small, and good and stable developability and images can be obtained even with long-term stirring in the developing device. can get.
When the toner is used for a two-component developer, it may be used by mixing with the carrier. The content of the carrier in the two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose. It is preferably 90% by mass to 98% by mass, and 93% by mass to 97% by mass. More preferred.

<Career>
There is no restriction | limiting in particular as said carrier, Although it can select suitably according to the objective, What has a core material and the resin layer which coat | covers a core material is preferable.
−Core material−
There is no restriction | limiting in particular as a material of the said core material, According to the objective, it can select suitably, For example, 50 emu / g-90 emu / g manganese-strontium type material, manganese-magnesium type material, etc. are mentioned. . In order to ensure the image density, it is preferable to use a highly magnetized material such as iron powder of 100 emu / g or more and magnetite of 75 emu / g to 120 emu / g. In addition, since the impact of the developer in the standing state on the photoconductor can be alleviated and it is advantageous for high image quality, a low-magnetization material such as a copper-zinc system of 30 emu / g to 80 emu / g should be used. Is preferred.
These may be used individually by 1 type and may use 2 or more types together.
There is no restriction | limiting in particular as a volume average particle diameter of the said core material, Although it can select suitably according to the objective, 10 micrometers-150 micrometers are preferable, and 40 micrometers-100 micrometers are more preferable. When the volume average particle diameter is less than 10 μm, fine powder is increased in the carrier, and magnetization per particle may be reduced to cause scattering of the carrier. In the case of a full color with many solid portions, reproduction of the solid portions may be deteriorated.

EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not limited to these. “Part” represents part by mass.
In the following Table 1-1 to Table 1-3 (these are collectively referred to as Table 1), the constituent materials of the amorphous polyester resins A, B and C, the crystalline polyester resins D and WAX, and the physical property values are shown. . Tables 2-1 to 2-3 below (also collectively referred to as Table 2) show the composition ratios of the amorphous polyester resins A, B and C, and the crystalline polyester resins D and WAX. The evaluation results of each example are shown in the following Table 3-1 to Table 3-3 (these are collectively referred to as Table 3).

<Preparation of toner component>
<< Synthesis of ketimine >>
170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged into a reaction vessel equipped with a stirrer and a thermometer, and reacted at 50 ° C. for 5 hours to obtain [ketimine compound 1]. The amine value of [ketimine compound 1] was 418.

<< Synthesis of Amorphous Polyester Resin A >>
-Synthesis of Amorphous Polyester Resin A-1-
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction pipe, OH which is a molar ratio of hydroxyl group to carboxyl group is 3-methyl-1,5-pentanediol, isophthalic acid, adipic acid, trimellitic anhydride / COOH is 1.5, the composition of the diol component is 100 mol% of 3-methyl-1,5-pentanediol, the composition of the dicarboxylic acid component is 40 mol% of isophthalic acid, 60 mol% of adipic acid, and trimellitic anhydride in all monomers Titanium tetraisopropoxide (1000 ppm vs. resin component) was added so that the amount of acid was 1 mol%. Thereafter, the temperature was raised to 200 ° C. in about 4 hours, and then the temperature was raised to 230 ° C. over 2 hours, and the reaction was carried out until there was no effluent water. Thereafter, the reaction was carried out at a reduced pressure of 10 mmHg to 15 mmHg for 5 hours to obtain an intermediate polyester. Next, an intermediate polyester and isophorone diisocyanate are charged at a molar ratio of 2.0 in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and diluted to 50% by mass with ethyl acetate. It was made to react at 5 degreeC for 5 hours, and prepolymer A-1 was obtained.
The amount of the amine of [ketimine compound 1] is equimolar with respect to the amount of isocyanate in the prepolymer while stirring the obtained prepolymer in a reaction vessel equipped with a heating device, a stirrer and a nitrogen introduction tube. Was added dropwise, and the prepolymer extension was taken out after stirring at 45 ° C. for 10 hours.
The obtained prepolymer extension product was dried under reduced pressure at 50 ° C. until the amount of residual ethyl acetate was 100 ppm or less to obtain amorphous polyester resin A-1. Table 1 shows the physical property values of the obtained amorphous polyester resin A-1.

<< Synthesis of Amorphous Polyester Resin B >>
-Synthesis of Amorphous Polyester Resin B-1-
A four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was mixed with bisphenol A ethylene oxide side 2 mol adduct / bisphenol A propylene oxide 2 mol adduct in a molar ratio of 85/15, 5- Sodium sulfoisophthalate, isophthalic acid, and adipic acid in a molar ratio of 5/75/20, OH / COOH, which is the molar ratio of hydroxyl group to carboxyl group, was charged in 1.3, and atmospheric pressure with 500 ppm of titanium tetraisopropoxide At 230 ° C. for 8 hours, and further reacted at a reduced pressure of 10 mmHg to 15 mmHg for 4 hours. Then, trimellitic anhydride is added to the reaction vessel so as to be 1 mol% with respect to all resin components, and 180 ° C. and normal pressure for 3 hours. By reacting, an amorphous polyester resin B-1 was obtained. The physical property values are shown in Table 1.

-Synthesis of amorphous polyester resin B-2-
A four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was mixed with bisphenol A ethylene oxide side 2 mol adduct / bisphenol A propylene oxide 2 mol adduct in a molar ratio of 85/15, 5- Sodium sulfoisophthalate, isophthalic acid, and adipic acid in a molar ratio of 1/79/20, OH / COOH, which is the molar ratio of hydroxyl group to carboxyl group, was charged in 1.3, and 500 ppm of titanium tetraisopropoxide was used at normal pressure At 230 ° C. for 8 hours, and further reacted at a reduced pressure of 10 mmHg to 15 mmHg for 4 hours. Then, trimellitic anhydride is added to the reaction vessel so as to be 1 mol% with respect to all resin components, and 180 ° C. and normal pressure for 3 hours. By reacting, an amorphous polyester resin B-2 was obtained. The physical property values are shown in Table 1.

-Synthesis of amorphous polyester resin B-3-
A four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was mixed with bisphenol A ethylene oxide side 2 mol adduct / bisphenol A propylene oxide 2 mol adduct in a molar ratio of 85/15, 5- Sodium sulfoisophthalate, isophthalic acid, and adipic acid in a molar ratio of 10/70/20, OH / COOH, which is the molar ratio of hydroxyl group to carboxyl group, was charged in 1.3, and atmospheric pressure with 500 ppm of titanium tetraisopropoxide At 230 ° C. for 8 hours, and further reacted at a reduced pressure of 10 mmHg to 15 mmHg for 4 hours. Then, trimellitic anhydride is added to the reaction vessel so as to be 1 mol% with respect to all resin components, and 180 ° C. and normal pressure for 3 hours. By reacting, an amorphous polyester resin B-3 was obtained. The physical property values are shown in Table 1.

-Synthesis of amorphous polyester resin B-4-
A four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was mixed with bisphenol A ethylene oxide side 2 mol adduct / bisphenol A propylene oxide 2 mol adduct in a molar ratio of 85/15, 5- Sodium sulfoisophthalate, isophthalic acid, and adipic acid in a molar ratio of 0.5 / 79.5 / 20, OH / COOH which is the molar ratio of hydroxyl group to carboxyl group was charged in 1.3, and 500 ppm of titanium tetraisopropoxy And reacted at 230 ° C. for 8 hours at normal pressure and further for 4 hours at a reduced pressure of 10 mmHg to 15 mmHg. Then, trimellitic anhydride was added to the reaction vessel so as to be 1 mol% with respect to the total resin components, and 180 ° C. at normal temperature. The mixture was reacted for 3 hours under pressure to obtain amorphous polyester resin B-4. The physical property values are shown in Table 1.

-Synthesis of amorphous polyester resin B-5-
A four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was mixed with bisphenol A ethylene oxide side 2 mol adduct / bisphenol A propylene oxide 2 mol adduct in a molar ratio of 85/15, 5- Potassium sulfoisophthalate, isophthalic acid, and adipic acid in a molar ratio of 5/75/20, OH / COOH, which is the molar ratio of hydroxyl group to carboxyl group, was charged in 1.3, and atmospheric pressure with 500 ppm of titanium tetraisopropoxide At 230 ° C. for 8 hours, and further reacted at a reduced pressure of 10 mmHg to 15 mmHg for 4 hours. Then, trimellitic anhydride is added to the reaction vessel so as to be 1 mol% with respect to all resin components, and 180 ° C. and normal pressure for 3 hours. By reacting, an amorphous polyester resin B-5 was obtained. The physical property values are shown in Table 1.

-Synthesis of amorphous polyester resin B-6-
A four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was mixed with bisphenol A ethylene oxide side 2 mol adduct / bisphenol A propylene oxide 2 mol adduct in a molar ratio of 85/15, 5- Sodium sulfoisophthalate, isophthalic acid, and adipic acid in a molar ratio of 0.65 / 79.35 / 20, OH / COOH, which is the molar ratio of hydroxyl group to carboxyl group, was charged in 1.3, and 500 ppm of titanium tetraisopropoxy And reacted at 230 ° C. for 8 hours at normal pressure and further for 4 hours at a reduced pressure of 10 mmHg to 15 mmHg. The mixture was reacted for 3 hours under pressure to obtain amorphous polyester resin B-6. The physical property values are shown in Table 1.

<< Synthesis of Amorphous Polyester Resin C >>
-Synthesis of Amorphous Polyester Resin C-1-
A four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, bisphenol A ethylene oxide side 2 mol adduct / bisphenol A propylene oxide 2 mol adduct in a molar ratio of 85/15, terephthalic acid And adipic acid at a molar ratio of 80/20, OH / COOH, which is the molar ratio of hydroxyl group to carboxyl group, was charged at 1.3, and reacted with 500 ppm of titanium tetraisopropoxide at 230 ° C. at normal pressure for 8 hours. Furthermore, after reacting at a reduced pressure of 10 mmHg to 15 mmHg for 4 hours, trimellitic anhydride was added to the reaction vessel at 1 mol% with respect to all resin components, and reacted at 180 ° C. for 3 hours at normal pressure. -1 was obtained. The physical property values are shown in Table 1.

<< Synthesis of Crystalline Polyester Resin D >>
-Synthesis of crystalline polyester resin D-1-
In a 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, OH / COOH which is the molar ratio of hydroxyl group to carboxyl group is 0.9, and the composition ratio of the acid component is dodecane The composition ratio of the acid 100 mol% and the alcohol component is 1,6-hexanediol 100 mol%. After reacting with 500 ppm of titanium tetraisopropoxide at 180 ° C. for 10 hours, the temperature is raised to 200 ° C. and reacted for 3 hours. Further, the reaction was performed at a pressure of 8.3 kPa for 2 hours to obtain a crystalline polyester resin D-1. The physical property values are shown in Table 1.

Example 1
<Manufacture of toner 1>
-Synthesis of master batch (MB)-
1,200 parts of water, 500 parts of PR269 (manufactured by Dainichi Seika), and 500 parts of amorphous polyester resin C-1 are added and mixed with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). After kneading at 150 ° C. for 30 minutes, rolling and cooling and pulverization with a pulverizer gave [Masterbatch 1].

-Preparation of WAX dispersion-
Paraffin wax 50 parts (manufactured by Nippon Seiki Co., Ltd., HNP-9, hydrocarbon wax, melting point 75 ° C., SP value 8.8) as a mold release agent 1 in a container equipped with a stir bar and a thermometer, and ethyl acetate 450 The temperature was raised to 80 ° C. with stirring and held at 80 ° C. for 5 hours, then cooled to 30 ° C. in 1 hour, and using a bead mill (Ultra Visco Mill, manufactured by IMEX Co., Ltd.), the liquid feeding speed was 1 kg. / Hr, disk peripheral speed 6 m / sec, 0.5 mm zirconia beads were filled at 80% by volume, and dispersion was performed under the conditions of 3 passes to obtain [WAX dispersion].

-Preparation of crystalline polyester dispersion 1-
50 parts of crystalline polyester D-1 and 450 parts of ethyl acetate are charged in a container equipped with a stir bar and a thermometer, heated to 80 ° C. with stirring, held at 80 ° C. for 5 hours, and then 30 for 1 hour. Cooled to ℃, using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), liquid feed speed 1 kg / hr, disk peripheral speed 6 m / sec, filled with 80% by volume of 0.5 mm zirconia beads, under the condition of 3 passes, Dispersion was performed to obtain [Crystalline Polyester Dispersion 1].

<< Preparation of oil phase >>
[WAX dispersion] 500 parts, [Prepolymer A-1] 300 parts, [Amorphous polyester resin B-1] 100 parts, [Amorphous polyester resin C-1] 550 parts, [Crystalline polyester resin dispersion] [Liquid 1] 500 parts, [Masterbatch 1] 100 parts and [ketimine compound 1] 2 parts are put in a container and mixed with a TK homomixer (manufactured by Tokushu Kika) at 5,000 rpm for 60 minutes. [Oil phase 1] Got.
Table 2-1 shows the mass ratio of each component and the content of the sulfo-substituted benzenedicarboxylic acid metal salt (SO ₃ metal salt content).

-Preparation of styrene / acrylic resin fine particles-
In a reaction vessel in which a stir bar and a thermometer were set, 683 parts of water, 16 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 83 parts of styrene, 83 parts of methacrylic acid, When 110 parts of butyl acrylate and 1 part of ammonium persulfate were added and stirred at 400 rpm for 15 minutes, a white emulsion was obtained. The system was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, and an aqueous vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). A dispersion [styrene / acryl resin fine particle dispersion] was obtained. [Styrene / acrylic resin fine particle dispersion] had a volume average particle size (measured with LA-920, manufactured by Horiba, Ltd.) of 14 nm, an acid value of 45 mgKOH / g, a molecular weight Mw of 300,000, and a Tg of 60 ° C.

-Preparation of acrylic resin fine particles a-
In a reaction vessel equipped with a stir bar and thermometer, 683 parts of water, 10 parts of distearyldimethylammonium chloride (cation DS, manufactured by Kao), 176 parts of methyl methacrylate, 18 parts of butyl acrylate, 1 part of ammonium persulfate, ethylene glycol When 2 parts of dimethacrylate was charged and stirred at 400 rpm for 15 minutes, a white emulsion was obtained. The mixture was heated to raise the temperature in the system to 65 ° C. and reacted for 10 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added and aged at 75 ° C. for 5 hours to obtain an aqueous dispersion of vinyl resin (methyl methacrylate) [acrylic resin fine particle dispersion a]. [Acrylic resin fine particles a] had a volume average particle size (measured with LA-920 manufactured by Horiba, Ltd.) of 35 nm, an acid value of 2 mgKOH / g, a molecular weight Mw of 30,000, and a Tg of 82 ° C.

<< Preparation of aqueous medium phase >>
660 parts by mass of water, 25 parts by mass of the above styrene / acrylic resin fine particle dispersion, 25 parts by mass of an aqueous solution of 48.5% by mass of sodium dodecyl diphenyl ether disulfonate (“Eleminol MON-7”; manufactured by Sanyo Chemical Industries), and ethyl acetate 60 parts by mass was mixed and stirred, and 50 parts by mass of acrylic resin fine particles a were added to obtain a milky white liquid [aqueous phase 1].

<< Emulsification / Desolvation >>
1,200 parts of [Aqueous phase 1] was added to the container containing [Oil phase 1], and mixed with a TK homomixer at a rotation speed of 8,000 rpm for 5 minutes to obtain [Emulsion slurry 1].
[Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was carried out at 45 ° C. for 4 hours to obtain [Dispersion slurry 1].

<< Washing and drying >>
[Dispersion Slurry 1] After filtering 100 parts under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered.
(2): 100 parts of a 10% aqueous sodium hydroxide solution was added to the filter cake of (1), mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
(3): 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(4): The operations of (1) to (4) above, wherein 300 parts of ion-exchanged water is added to the filter cake of (3), mixed with a TK homomixer (10 minutes at 12,000 rpm) and then filtered. Was performed twice to obtain [Filter cake 1].
The obtained [Filtration cake 1] was dried at 45 ° C. for 48 hours using a circulating dryer, and sieved with a mesh having a mesh size of 75 μm to obtain toner base particles.
To 100 parts of the obtained toner base particles, 1.0 part of hydrophobic silica as an external additive and 0.5 part of hydrophobic titanium oxide are added and mixed using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). As a result, toner particles [Toner 1] were obtained.

<Preparation of developer>
Using a ball mill, 5 parts of [Toner 1] and 95 parts of the following carrier were mixed to prepare a developer.
-Production of carrier-
Add 100 parts of silicone resin organostraight silicone, 5 parts of γ- (2-aminoethyl) aminopropyltrimethoxysilane, and 10 parts of carbon black to 100 parts of toluene, disperse with a homomixer for 20 minutes, and apply resin layer A liquid was prepared. Using a fluidized bed type coating apparatus, the resin layer coating solution was applied to the surface of 1,000 parts of spherical magnetite having an average particle size of 50 μm to prepare a carrier.
Next, various characteristics were evaluated using the produced developer as follows. The results are shown in Table 3-1.

<Low-temperature fixability and high-temperature offset property>
A copying test was performed on type 6200 paper (manufactured by Ricoh Co., Ltd.) using an apparatus in which a fixing unit of a copying machine MF2200 (manufactured by Ricoh Co., Ltd.) using a Teflon (registered trademark) roller as a fixing roller was modified.
Specifically, the cold offset temperature (fixing lower limit temperature) and the high temperature offset temperature (fixing upper limit temperature) were determined by changing the fixing temperature.
The evaluation conditions for the minimum fixing temperature were a paper feed linear velocity of 120 mm to 150 mm / second, a surface pressure of 1.2 kgf / cm ² , and a nip width of 3 mm.
The evaluation conditions for the upper limit fixing temperature were a paper feed linear velocity of 50 mm / second, a surface pressure of 2.0 kgf / cm ² , and a nip width of 4.5 mm.
[Evaluation criteria for fixability (fixing lower limit)]
○: 110 ° C. or less Δ: 115 ° C. to 130 ° C.
×: 135 ° C or higher

<Image density>
About each obtained developer, the adhesion amount of each developer is 1. on the copy paper (TYPE6000 <70W>, manufactured by Ricoh Co., Ltd.) using a tandem type color electrophotographic apparatus (image Neo 450, manufactured by Ricoh Co., Ltd.). A solid image of 00 ± 0.05 mg / cm ² was formed. The solid image was repeatedly formed on 8,000 copy sheets. The image density of the obtained solid image was visually observed at the initial stage and after endurance of 8,000 sheets, and evaluated based on the following criteria. The higher the image density obtained, the higher the density image can be formed.
〔Evaluation criteria〕
◯: There was no change in image density and high image quality was obtained at the initial stage and after endurance of 8,000 sheets.
[Delta]: After 8,000 sheets were used, the image density was slightly lowered and the image quality was lowered.
X: After the endurance of 8,000 sheets, the image density was remarkably lowered and the image quality was greatly lowered.

<Heat resistant storage stability>
The toner was stored at 50 ° C. for 8 hours and then sieved with a 42 mesh sieve for 2 minutes, and the residual rate on the wire mesh was measured. At this time, the toner having better heat-resistant storage stability has a smaller remaining rate.
The evaluation criteria for heat resistant storage stability were as follows.
〔Evaluation criteria〕
◎: Residual rate is less than 10% ○: Residual rate is 10% or more and less than 20% △: Residual rate is 20% or more and less than 30% ×: Residual rate is 30% or more

<Transfer White>
The developer was mounted on Imagio MP C2802 (manufactured by Ricoh Co., Ltd.), and 10,000 A4 images with an image area ratio of 5% were continuously printed. After the test was completed, three solid images (toner adhesion amount: 0.4 mg / cm ² ) were output on A4 paper, and the number of blank images in the image was visually measured.
The following ranking was performed based on the total number of three blank images.
[Rank]
A: The blank images are not visually recognized in all three sheets.
○: The third blank image can be confirmed by observing with an optical microscope, but this is not a practically problematic level.
Δ: 1 to 10 blank images can be visually confirmed by combining the three images, and there is a practical problem.
×: Over 10 images of white spots can be visually confirmed by combining 3 images, and there is a large problem level in practical use.

<Cleanability>
Using a full-color laser complex machine Imagio Neo C600pro (manufactured by Ricoh Co., Ltd.), running 2,000 image charts with a 100% image area in monochromatic mode, and then running the toner on the photoreceptor that passed through the cleaning blade to the scotch tape ( The product was transferred to white paper with Sumitomo 3M Co., Ltd., and the density was measured with a colorimeter X-Rite 938 (manufactured by X-Rite).
〔Evaluation criteria〕
◎: When the difference from the blank is less than 0.003 ○: When the difference from the blank is 0.003-0.01 △: When the difference from the blank is 0.011-0.02 ×: With the blank When the difference is 0.021 to 0.03 XX: When the difference from the blank exceeds 0.031

(Example 2)
[Toner 2] of Example 2 was obtained in the same manner as in Example 1 except that the amorphous polyester resin B-1 of Example 1 was changed to amorphous polyester resin B-2.
The toner 2 was evaluated in the same manner as in Example 1.
Table 1-1, Table 2-1, and Table 3-1 show the physical property values, the composition ratio, and the results of the evaluations regarding the toner of Example 2.

(Example 3)
[Toner 3] of Example 3 was obtained in the same manner as in Example 1 except that the amorphous polyester resin B-1 of Example 1 was changed to an amorphous polyester resin B-3.
The toner 3 was evaluated in the same manner as in Example 1.
Table 1-1, Table 2-1, and Table 3-1 show the physical property values, the composition ratio, and the results of the respective evaluations regarding the toner of Example 3.

Example 4
[Toner 4] of Example 4 was obtained in the same manner as in Example 1 except that the amorphous polyester resin B-1 of Example 1 was changed to an amorphous polyester resin B-4.
The toner 4 was evaluated in the same manner as in Example 1.
Table 1-1, Table 2-1, and Table 3-1 show the physical property values, the composition ratio, and the results of the evaluations regarding the toner of Example 4.

(Example 5)
[Toner 5] of Example 5 was obtained in the same manner as in Example 1 except that the amorphous polyester resin B-1 of Example 1 was changed to amorphous polyester resin B-5.
The toner 5 was evaluated in the same manner as in Example 1.
Tables 1-2, 2-2, and 3-2 show the physical property values, composition ratios, and results of the respective evaluations regarding the toner of Example 5.

(Example 6)
[Toner 6] of Example 6 was obtained in the same manner except that 700 parts of [Prepolymer A-1] and 350 parts of [Amorphous polyester resin C-1] were changed in the preparation of the oil phase of Example 1. It was.
The toner 6 was evaluated in the same manner as in Example 1.
Tables 1-2, 2-2, and 3-2 show the physical property values, composition ratios, and results of the respective evaluations regarding the toner of Example 6.

(Example 7)
[Toner 7] of Example 7 was obtained in the same manner as in the preparation of the oil phase of Example 1, except that [Prepolymer A-1] was changed to 100 parts and [Amorphous polyester resin C-1] was changed to 650 parts. It was.
The toner 7 was evaluated in the same manner as in Example 1.
Tables 1-2, 2-2, and 3-2 show the physical property values, composition ratios, and results of the respective evaluations regarding the toner of Example 7.

(Example 8)
[Toner 8] of Example 8 was obtained in the same manner except that 50 parts of [Prepolymer A-1] and 675 parts of [Amorphous polyester resin C-1] were changed in the preparation of the oil phase of Example 1. It was.
The toner 8 was evaluated in the same manner as in Example 1.
Tables 1-2, 2-2, and 3-2 show the physical property values, composition ratios, and results of the respective evaluations regarding the toner of Example 8.

(Comparative Example 1)
[Toner 9] of Comparative Example 1 was prepared in the same manner as in the preparation of the oil phase of Example 1, except that 0 part of [Amorphous Polyester Resin B-1] and 650 parts of [Amorphous Polyester Resin C-1] were used. ]
The toner 9 was evaluated in the same manner as in Example 1.
Tables 1-3, 2-3, and 3-3 show the physical property values, composition ratios, and results of the evaluations regarding the toner of Comparative Example 1.

(Comparative Example 2)
[Toner 10 of Comparative Example 2] was prepared in the same manner as in the preparation of the oil phase of Example 1, except that 0 part of [amorphous polyester resin C-1] and 700 parts of [amorphous polyester resin B-6] were used. ]
The toner 10 was evaluated in the same manner as in Example 1.
Tables 1-3, 2-3, and 3-3 show the physical property values, the composition ratio, and the results of the evaluations regarding the toner of Comparative Example 2.

(Comparative Example 3)
[Toner 11] of Comparative Example 3 was obtained in the same manner as in the preparation of the oil phase of Example 1, except that 0 part of [Prepolymer A-1] and 700 parts of [Amorphous Polyester Resin C-1] were used. It was.
The toner 11 was evaluated in the same manner as in Example 1.
Tables 1-3, 2-3, and 3-3 show the physical property values, the composition ratio, and the results of the evaluations regarding the toner of Comparative Example 3.

(Comparative Example 4)
[Toner 12] of Comparative Example 4 was prepared in the same manner as in the preparation of the oil phase of Example 1, except that 0 part of [crystalline polyester resin D-1] and 600 parts of [amorphous polyester resin C-1] were used. Got.
The toner 12 was evaluated in the same manner as in Example 1.
Tables 1-3, 2-3, and 3-3 show the physical property values, the composition ratio, and the results of the evaluations regarding the toner of Comparative Example 4.

(Comparative Example 5)
[Toner 13] of Comparative Example 5 was prepared in the same manner as in the preparation of the oil phase of Example 1, except that 0 part of [Amorphous Polyester Resin C-1] and 700 parts of [Amorphous Polyester Resin B-1] were used. ]
The toner 13 was evaluated in the same manner as in Example 1.
Tables 1-3, 2-3, and 3-3 show the physical property values, the composition ratio, and the results of the evaluations regarding the toner of Comparative Example 5.

Aspects of the present invention are as follows, for example.
<1> In a toner containing at least a colorant, a binder resin, and a release agent,
The binder resin contains a polyester resin,
The polyester resin, the constituent acid monomer comprises a sulfo-substituted benzene dicarboxylic acid metal salt,
The toner has an average circularity of 0.940 to 0.970.
<2> The polyester resin is composed of at least three types of amorphous polyester resins A, B, and C, and a crystalline polyester resin.
The amorphous polyester resin A is a resin having a glass transition temperature of −60 ° C. or higher and lower than 0 ° C., having a branched structure, and having either a urethane bond or a urea bond.
The amorphous polyester resins B and C have a glass transition temperature of 40 ° C. or higher and lower than 70 ° C., and the amorphous polyester resin B further includes a metal salt containing sulfo-substituted benzene dicarboxylic acid as a constituent acid monomer. The toner according to <1>.
<3> The content of the sulfo-substituted benzenedicarboxylic acid metal salt as an acid monomer constituting the polyester resin in the toner is from 0.1% by mass to 1.0% by mass, from <1> to <2 > The toner according to any one of the above.
<4> The toner according to any one of <1> to <3>, wherein the sulfo-substituted benzenedicarboxylic acid metal salt is sodium 5-sulfoisophthalate.
<5> The toner according to any one of <2> to <4>, wherein the total content of the amorphous polyester resins B and C in the toner is 50% by mass or more and 80% by mass or less.
<6> The toner according to any one of <2> to <5>, wherein the crystalline polyester resin has a melting point of 60 ° C. or higher and 80 ° C. or lower.
<7> The toner according to any one of <1> to <6>, wherein the toner contains a release agent having a melting point of 50 ° C. or higher and 90 ° C. or lower.
<8> The above <1> to <7, wherein the toner has a volume average particle diameter / number average particle diameter (Dv / Dn) of 1.25 or less and an average circularity of 0.940 or more and 0.955 or less. > The toner according to any one of the above.
<9> Step A in which a toner material containing at least a binder resin is dissolved or dispersed in an organic solvent to prepare a toner material dissolved or dispersed, and the toner material dissolved or dispersed in the aqueous medium. Any one of <1> to <8> manufactured by Step B of emulsifying or dispersing to prepare an emulsion or dispersion and Step C of removing an organic solvent from the emulsion or dispersion to prepare toner particles The toner described in 1.
<10> A developer comprising the toner according to any one of <1> to <9>.

Japanese Patent Laid-Open No. 11-133665 JP 2001-66827 A Japanese Patent No. 3661422 JP 2009-169383 A JP 2013-190644 A

Claims (10)

In a toner containing at least a colorant, a binder resin and a release agent,
The binder resin contains a polyester resin,
The polyester resin, the constituent acid monomer comprises a sulfo-substituted benzene dicarboxylic acid metal salt,
The toner having an average circularity of 0.940 to 0.970. The polyester resin comprises at least three kinds of amorphous polyester resins A, B and C, and a crystalline polyester resin,
The amorphous polyester resin A is a resin having a glass transition temperature of −60 ° C. or higher and lower than 0 ° C., having a branched structure, and having either a urethane bond or a urea bond.
The amorphous polyester resins B and C have a glass transition temperature of 40 ° C. or higher and lower than 70 ° C., and the amorphous polyester resin B further comprises a sulfo-substituted benzenedicarboxylic acid metal salt as a constituent acid monomer. Item 2. The toner according to Item 1.   3. The content of the sulfo-substituted benzenedicarboxylic acid metal salt as an acid monomer constituting the polyester resin in the toner is 0.1% by mass or more and 1.0% by mass or less. Toner.   The toner according to claim 1, wherein the sulfo-substituted benzenedicarboxylic acid metal salt is sodium 5-sulfoisophthalate.   The toner according to claim 2, wherein the total content of the amorphous polyester resins B and C in the toner is 50% by mass or more and 80% by mass or less.   The toner according to claim 2, wherein the crystalline polyester resin has a melting point of 60 ° C. or higher and 80 ° C. or lower.   The toner according to claim 1, wherein the toner contains a release agent having a melting point of 50 ° C. or higher and 90 ° C. or lower.   The volume average particle diameter / number average particle diameter (Dv / Dn) of the toner is 1.25 or less, and the average circularity is 0.940 or more and 0.955 or less. Toner.   A step A in which a toner material containing at least a binder resin is dissolved or dispersed in an organic solvent to prepare a toner material dissolved or dispersed, and the toner material dissolved or dispersed in the aqueous medium is emulsified or dispersed. The toner according to any one of claims 1 to 8, wherein the toner is produced by a step B for producing an emulsified or dispersed liquid and a step C for removing an organic solvent from the emulsified or dispersed liquid to produce toner particles. A developer comprising the toner according to claim 1.