JP2013190644A - Toner for image formation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner for image formation capable of simultaneously satisfying low energy fixability and room temperature shelf stability, while maintaining excellent toner quality such as formation of a high quality image, allowing uniform dispersion of a pigment in the toner, and enabling excellent image for a long period of time.SOLUTION: A toner includes at least a coloring agent, a binder resin and a release agent. The binder resin has at least two kinds of amorphous resins A, B and a crystalline resin. The amorphous resin A is a resin with a glass-transition temperature of -60°C or higher, and lower than 0°C, having a branched structure, and including an urethane or urea bond. The amorphous resin B has a glass-transition temperature of 40°C or higher, and lower than 70°C, and includes a unit obtained from sulfo substitution benzene dicarboxylic acid metal salt and one of esters thereof. A content of the unit in the toner is 0.05 through 4 wt%.

Description

  The present invention relates to a toner and a developer.

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) is likely to adhere 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, 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 (see, for example, Patent Documents 2, 3, and 4). .
However, in the methods described in these documents, the pigment dispersibility improvement in the toner obtained by the previous polymerization method is insufficient, and it is difficult to suppress aggregation and uneven distribution of pigment particles near the toner surface. .
We have already dispersed the toner phase containing the toner material in an aqueous medium or emulsified to form toner base particles, such as preventing uneven distribution of pigment near the surface of the toner base particles. In order to promote dispersion, it has been proposed to use a pigment dispersant having substantially no ionic group (both acid value and amine value are 1 mg KOH / g or less) -54669).

  In the present invention, the pigment is uniformly dispersed in the toner while maintaining good toner quality such as low energy fixability and storage at room temperature at the same time, and high-quality image formation is possible. An object of the present invention is to provide an image forming toner capable of obtaining an image.

In order to solve the above problems, the present inventors have completed the inventions described in the following items (1) to (13).
(1) In a toner containing at least a colorant, a binder resin and a release agent, the binder resin comprises at least two types of amorphous resins A and B and a crystalline resin, and the amorphous resin A is The resin having a glass transition temperature of −60 ° C. or higher and lower than 0 ° C., having a branched structure, and having a urethane or urea bond, the amorphous resin B has a glass transition temperature of 40 ° C. or higher and 70 ° C. And a unit obtained from any one of a sulfo-substituted benzenedicarboxylic acid metal salt and an ester thereof, and the content of the unit in the toner is 0.05% to 4% by weight. Toner.
(2) The toner according to item (1), wherein the amorphous resins A and B and the crystalline resin are amorphous polyester resins A and B and a crystalline polyester resin, respectively. 3) The content of a unit obtained from any one of the sulfo-substituted benzenedicarboxylic acid metal salt and the ester thereof in the resin B is 0.1 wt% to 5 wt% (Item 1) Or the toner according to item (2).
(4) The toner according to any one of (1) to (3), wherein the sulfo-substituted benzenedicarboxylic acid metal salt and ester thereof are sodium salts.
(5) The toner according to any one of (1) to (4), wherein the sulfo-substituted benzenedicarboxylic acid metal salt is sodium 5-sulfoisophthalate.
(6) The toner according to any one of (1) to (5), wherein the content of the resin B in the toner is 50 wt% or more and less than 90 wt%.
(7) The toner according to any one of (1) to (6), wherein the content of the resin A in the toner is 5 wt% or more and less than 25 wt%.
(8) The items (1) to (7), wherein the crystalline polyester includes a crystalline polyester having a melting point of 60 ° C. or higher and lower than 80 ° C., and Tg1st-Tg2nd of the toner is 10 ° C. or higher. The toner according to any one of the above.
(9) The toner particles of the toner are composed of core particles composed of a colorant, a binder resin, and a release agent, and a resin layer formed on the outside of the core particles, and the resin layer is composed of at least styrene / acrylic resin fine particles. The toner according to any one of (1) to (8) above, which comprises a layer I and a layer E made of acrylic resin fine particles.
(10) The toner according to any one of (1) to (9) above, which contains a release agent having a melting point of 50 ° C. or higher and lower than 90 ° C.
(11) An image forming developer comprising the toner according to any one of (1) to (10).
The present invention also includes the following “toner” and “toner production method”.
(12) An organic solvent liquid obtained by dissolving or dispersing a toner material containing at least a binder resin is emulsified or dispersed in an aqueous medium to remove the organic solvent to prepare toner particles. The toner according to any one of (1) to (10), wherein the toner is a toner.
(13) A method for chemically producing a toner, wherein an organic solvent liquid obtained by dissolving or dispersing a toner material containing at least a binder resin is emulsified or dispersed in an aqueous medium to produce an emulsified or dispersed liquid. And a step of producing toner particles by removing the organic solvent, wherein the toner particles contain at least a colorant, a binder resin, and a release agent, and the binder resin comprises at least two amorphous materials. The amorphous resin A is a resin having a glass transition temperature of −60 ° C. or higher and lower than 0 ° C., a branched structure, and a urethane or urea bond. The amorphous resin B is a resin having a glass transition temperature of 40 ° C. or higher and lower than 70 ° C., and includes a unit obtained from any one of sulfo-substituted benzene dicarboxylic acid metal salts and their esters, and Previous Method for producing a toner, wherein the content of said unit in the toner particles is 0.05% to 4 wt%.

  According to the present invention, the pigment is uniformly dispersed in the toner while maintaining the toner quality such as the temperature range of the fixing upper limit temperature and the fixing lower limit temperature, storage resistance, low filming property, and pigment dispersibility, over a long period of time. A toner that outputs a good image can be provided.

  Below, the form for implementing this invention is demonstrated. Note that it is easy for a person skilled in the art to make other embodiments by changing or correcting the present invention within the scope of the claims, and these changes and modifications are included in the scope of the claims. The following description is intended to facilitate understanding of the present invention and does not limit the scope of the claims.

<Amorphous resins A and B>
The image forming toner of the present invention (hereinafter simply referred to as “toner”) contains at least two types of amorphous resins A and B as binder resins. In particular, the at least two types of amorphous resins include a resin A having a non-linear branched structure and having a urethane or urea bond, and a resin B having a linear structure.
Since the resin A has a very low glass transition temperature, it has a property of being deformed at a low temperature, a property of being deformed by heating and pressurizing at the time of fixing, and a property of being easily adhered to paper at a lower temperature. In addition, since it has urethane and urea bonds with high cohesive energy, it has excellent adhesion to paper. In addition, because the toner molecular skeleton has a branched structure, and the urethane and urea bonding sites with high cohesive energy behave like pseudo-crosslinking points, the molecular chain becomes a three-dimensional network structure and deforms at low temperatures. Since it has a rubber-like property that it does not, it is possible to maintain the heat-resistant storage stability and high-temperature offset property of the toner.

  In other words, the glass transition temperature of the toner is set lower than before by combining the resin A, which has a glass transition temperature in an ultra-low temperature range but has a high melt viscosity and is difficult to flow, with another resin B in a compatible state. In addition, heat resistance storage stability and offset resistance can be maintained, and both low-temperature fixability can be achieved.

[Amorphous resin A]
The amorphous resin A will be described.
The amorphous resin A is preferably a polyester resin composed of a nonlinear reactive precursor a having a branched structure and a curing agent. Therefore, hereinafter, the case where the amorphous resin A is a polyester resin will be mainly described.
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 resin A of the present invention preferably has a temperature of −60 ° C. or higher and lower than 0 ° C. according to a glass transition temperature measuring method described later. When the temperature is less than -60 ° C, the flow of toner at low temperature cannot be suppressed, and the heat resistant storage stability is deteriorated. When the temperature is 0 ° C. or higher, the toner is not sufficiently deformed by heating and pressing during fixing, and the low-temperature fixability is poor.
The amorphous polyester resin 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. For example, 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 including ethylene oxide and propylene oxide Alkylene oxides such as butylene oxide; bisphenols such as bisphenol A, bisphenol F, and bisphenol S; alkylene oxides of bisphenols such as those obtained by adding alkylene oxide such as ethylene oxide, propylene oxide, and butylene oxide to bisphenols Adducts; and the like. Among these, in order to make it easy to impart a property of low Tg and deformation at a low temperature, it is preferable to contain an aliphatic diol having 4 or more and less than 12 carbon atoms in an amount of 50 wt% or more in the total dicarboxylic acid component.

[Dicarboxylic acid]
There is no restriction | limiting in particular as 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 an aliphatic dicarboxylic acid having 4 to 12 carbon atoms in an amount of 50 wt% or more of the total dicarboxylic acid component.

[Trivalent or higher acid or alcohol]
A conventionally known trivalent or higher alcohol can be used as a non-linear component, that is, a component for taking a branched structure.
Examples of the 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.

As an isocyanate component, as a diisocyanate, C6-C20 aromatic diisocyanate, C2-C18 aliphatic diisocyanate, C4-C15 alicyclic (except the carbon in a NCO group). Diisocyanates, araliphatic diisocyanates having 8 to 15 carbon atoms and modified products of these diisocyanates (urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, oxazolidone group-containing modification) And a mixture 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 weight) of a trifunctional or higher functional polyamine] phosgenate: polyallyl polyisocyanate (PAPI)], 1,5-naphthylene diisocyanate, 4,4 ′, 4 ″ -Triphenylmethane triisocyanate, m- and p-isocyanatov Such as sulfonyl 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.

  Of 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, HDI and water. Attached MDI and IPDI.

As the curing agent that reacts with isocyanate, a conventionally known amine compound can be suitably used.
Examples of diamines (including trivalent 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 [methylene bis-o-chloroaniline, 4-chloro-] having a nucleus-substituted electron withdrawing group (halogen such as Cl, Br, I, F; alkoxy group such as methoxy and ethoxy; nitro group, etc.) 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) propa Bis (4-amino-2-chlorophenyl) sulfone, bis (4-amino-3-methoxyphenyl) decane, bis (4-aminophenyl) sulfide, bis (4-aminophenyl) telluride, bis (4-aminophenyl) ) 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, A lower alkyl group such as ethyl)] [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 mol of acid) polyamine (the above-mentioned alkylene diamine, polyalkylene polyamine 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 resin A is preferably 20,000 or more and less than 1,000,000. The average molecular weight of the 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 less than 20,000, the toner tends to flow at a low temperature and the heat resistant storage stability may be inferior. Moreover, the viscosity at the time of melting may be low, and the high temperature offset property may be inferior.

[Amorphous resin B]
The amorphous resin B is also preferably a polyester resin. Therefore, hereinafter, the case where the amorphous resin B is a polyester resin will be mainly described.
When the amorphous resin B is linear and is a polyester resin, the amorphous resin B is obtained using a diol component and a dicarboxylic acid, and obtained from any one of the sulfo-substituted benzenedicarboxylic acid metal salts and esters thereof. Contributes to pigment dispersibility. Further, as will be understood from the specific examples described later, when the amorphous polyester resin A and the crystalline polyester resin are used in combination, surprisingly, the pigment dispersibility is hardly inhibited or offset.

  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 alone or in combination of two or more. Of these, sodium salts are preferable, and sodium 5-sulfoisophthalate is particularly preferable.

The content of units obtained from any one selected from the sulfo-substituted benzenedicarboxylic acid metal salts in the toner is preferably 0.05 wt% or more and less than 4 wt%. If it is less than 0.05 wt%, the effect on the pigment dispersibility is low, and if it exceeds 4 wt%, the viscosity increases and the toner fixing characteristics deteriorate.
Means for adjusting the content of units obtained from any one selected from the sulfo-substituted benzenedicarboxylic acid metal salts in the toner include the content of the sulfoisophthalic acid metal salts in the amorphous polyester resin B and the The content of the amorphous polyester resin B in the toner may be adjusted.

  The content of the unit obtained from any one of the sulfo-substituted benzenedicarboxylic acid metal salts in the amorphous polyester resin B is preferably 0.1 wt% or more and less than 5 wt%. If it is less than 0.1 wt%, the effect on the pigment dispersibility is not sufficient, and if it exceeds 5 wt%, the melt viscosity of the resin increases, which adversely affects the toner fixing characteristics.

  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 weight of the resin B is 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 and the durability against stress such as stirring in the developing device can be achieved. 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. Therefore, in GPC measurement, the weight average molecular weight (Mw) is 3,000 to 10,000, The number average molecular weight (Mn) is preferably 1,000 to 4,000, and Mw / Mn 1.0 to 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.

  There is no restriction | limiting in particular as an acid value of the said resin B, Although it can select suitably according to the objective, 1 mgKOH / g-50 mgKOH / g are preferable, and 5 mgKOH / g-30 mgKOH / g are 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 exceeds 50 mgKOH / g, the charging stability, particularly the charging stability against environmental fluctuations may be lowered.

  There is no restriction | limiting in particular as the hydroxyl value of the said resin B, 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 resin B is linear, and when the Tg of the polyester having no cross-linked structure is too low, the heat resistant storage stability of the toner and the durability against stresses such as stirring in the developing device can be obtained. Inferior, when Tg is too high, deformation due to heating and pressurization at the time of fixing the toner is insufficient, so that low temperature fixability is inferior.

The molecular structure of the resin B can be confirmed by X-ray diffraction, GC / MS, LC / MS, IR measurement, etc., in addition to NMR measurement by solution or solid. For convenience, the resin is dissolved in a mixed solvent of trifluoroacetic acid / deuterated chloroform = 1/1, then the nuclear magnetic resonance spectrum ( ¹ H-NMR) is measured, and the molecular structure is confirmed from the spectrum pattern according to a conventional method. Methods and the like.

(Crystalline resin)
Since the crystalline resin has high crystallinity, it exhibits a heat-melting characteristic that shows a rapid viscosity drop near the fixing start temperature. By using the crystalline resin having such characteristics together with the amorphous 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 viscosity is rapidly decreased due to melting of the crystalline resin (Sharp melt property) is generated, compatible with the amorphous resin, and fixed together by suddenly lowering the viscosity, so that a toner having both good heat storage stability and low temperature fixability can be obtained. . Also, good results are shown for the release width (difference between the fixing lower limit temperature and the hot offset occurrence temperature).

The crystalline resin is also preferably a polyester resin. Such a polyester resin is obtained by 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. Therefore, hereinafter, the case where the crystalline resin is a polyester resin will be mainly described.
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 less than 4 carbon atoms, when the polycondensation with the aromatic dicarboxylic acid is performed, the melting temperature becomes high, and low-temperature fixing may be difficult. On the other hand, when the number of carbon atoms exceeds 12, it becomes difficult to obtain practical materials. 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.

(Polyvalent carboxylic 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 less than 60 ° C., the crystalline polyester resin is easily melted at a low temperature and the heat-resistant storage stability of the toner may be lowered. When the melting point is 80 ° C. or more, the crystalline polyester resin is heated by fixing. Insufficient melting may cause low temperature fixability.

  The melting point can be measured by an endothermic peak value of a DSC chart in a differential scanning calorimeter (DSC) measurement.

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 example, 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 less than 2 parts by mass, the low-temperature fixability may be inferior because sharp melting by the crystalline polyester resin is insufficient, and when it exceeds 20 parts by mass, the heat-resistant storage stability is deteriorated. In addition, image fogging may occur easily. 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.

[Resin layer]
In the toner of the present invention, it is preferable that a resin layer is formed on the outside of the core particles made of a colorant, a binder resin, and a release agent. It is preferable that the resin layer includes at least a layer I made of styrene / acrylic resin fine particles and a layer E made of acrylic resin fine particles, and the layer I is outside the layer E.

  The resin constituting the styrene / acrylic resin fine particles is not particularly limited as long as it is a styrene / acrylic copolymer capable of forming an aqueous dispersion in an aqueous medium, and is appropriately selected from known resins according to the purpose. be able to. For example, styrene- (meth) acrylic ester resin, styrene-butadiene copolymer, (meth) acrylic acid-acrylic ester polymer, styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene- ( And a (meth) acrylic acid copolymer.

  Further, as the styrene / acrylic resin fine particles, a copolymer containing a monomer having at least two unsaturated groups can be used. The monomer having at least two unsaturated groups is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a sodium salt of ethylene oxide methacrylate adduct sulfate (“Eleminol RS-30”). "; Manufactured by Sanyo Chemical Industries Ltd.), divinylbenzene, 1,6-hexanediol acrylate and the like.

The volume average particle diameter of the styrene / acrylic resin fine particles is preferably 20 to 400 nm, and more preferably 30 to 350 nm. If the volume average particle diameter is less than 20 nm or exceeds 400 nm, the granulation behavior of the toner may become unstable.
The content of the styrene / acrylic resin fine particles in the toner particles is preferably 0.5 to 8.0% by mass, and more preferably 0.6 to 7.0% by mass. When the content is less than 0.5% by mass or more than 8.0% by mass, the granulation behavior of the toner may become unstable.

  The glass transition temperature of the styrene / acrylic resin is preferably 40 ° C. or higher and lower than 100 ° C. When the glass transition temperature is less than 40 ° C., the heat resistant storage stability is deteriorated, and when it is 100 ° C. or more, the fixing characteristics may be deteriorated.

  The resin constituting the acrylic resin fine particles is not particularly limited as long as it is an acrylic resin capable of forming an aqueous dispersion in an aqueous medium, and can be appropriately selected from known resins according to the purpose. For example, a homopolymer of acrylic acid, methacrylic acid or a derivative thereof and an ester thereof, or a copolymer composed of at least two of these monomers can be mentioned. In addition, a homopolymer or copolymer comprising a monomer having at least two unsaturated groups can be used. The monomer having at least two unsaturated groups is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ethylene glycol dimethacrylate.

  The volume average particle size of the acrylic resin fine particles is preferably 20 to 500 nm, and more preferably 30 to 450 nm. When the volume average particle size is less than 20 nm or exceeds 500 nm, the granulation behavior of the toner may become unstable.

  The content of the styrene / acrylic resin fine particles in the toner particles is preferably 0.5 to 8.0% by mass, and more preferably 0.6 to 7.0% by mass. When the content is less than 0.5% by mass, the heat-resistant storage stability is deteriorated, and when it exceeds 8.0% by mass, the granulation behavior of the toner may become unstable.

  The glass transition temperature of the styrene / acrylic resin is preferably 40 ° C. or higher and lower than 100 ° C. When the glass transition temperature is less than 40 ° C., the heat resistant storage stability is deteriorated, and when it is 100 ° C. or more, the fixing characteristics may be deteriorated.

〔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 60 ° C. or higher and lower than 80 ° C. When it is less than 60 ° C., the release agent is likely to melt at low temperatures, and the heat resistant storage stability may be inferior. When the temperature is 80 ° C. or higher, even when the binder resin of the present invention is melted and is in the fixing temperature range, the release agent may not be sufficiently melted to cause a fixing offset and may cause image loss.

  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 less than 2 parts by mass, the high-temperature offset resistance during fixing and the low-temperature fixability may be inferior. When the content exceeds 10 parts by mass, heat-resistant storage stability is deteriorated, and image fogging occurs. Etc. may occur easily. 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 lithopone.
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 B.

  The masterbatch can be obtained by mixing a masterbatch resin and a colorant under high shear 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>
There is no restriction | limiting in particular as said other component, According to the objective, it can select suitably, For example, a charge control agent, an external additive, a fluid improvement agent, a cleaning property improvement agent, a magnetic material etc. are mentioned.

[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 exceeds 10 parts by mass, the chargeability of the toner is too large, the effect of the main charge control agent is reduced, the electrostatic attraction force with the developing roller is increased, and the flowability of the developer is reduced. The image density may be reduced. 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 and hydrophobized inorganic particles can be used in combination, but the average particle size of the hydrophobized primary particles is preferably 1 nm to 100 nm, and 5 nm to 70 nm. The inorganic fine particles are more preferable.
Further, it is preferable that at least one kind of inorganic fine particles having an average particle diameter of 20 nm or less of the primary particles subjected to the hydrophobization treatment is contained, and at least one kind of inorganic fine particles having a diameter of 30 nm or more is 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 an 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 smaller than this range, the inorganic fine particles are buried in the toner, and the function is hardly exhibited effectively. On the other hand, if it is larger than this range, the surface of the photoreceptor is undesirably damaged.

[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.

As the glass transition temperature (Tg) of the toner, the glass transition temperature (Tg 1st) calculated at the first temperature increase in DSC measurement is preferably 18 ° C. or higher and lower 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 Tg 1st is less than 18 ° C., blocking and filming on the photoreceptor occur in the developing machine even when the resin of the present invention is used. When the temperature is 40 ° C. or higher, the low-temperature fixability of the toner is lowered.

The difference Tg1st−Tg2nd between the glass transition temperature (Tg2nd) calculated at the second temperature increase in the DSC measurement of the toner and Tg1st is preferably 10 ° C. or more.
In this case, crystalline polyester is incompatible with amorphous polyester before heating, and compatibility between amorphous polyester and crystalline polyester proceeds after heating. Excellent.

  The volume average particle diameter of the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 3 μm or more and 7 μm or less. The ratio of the volume average particle diameter to the number average particle diameter is preferably 1.2 or less. Further, it is preferable to contain 1% by number or more and 10% by number or less of a component having a volume average particle diameter of 2 μm or less.

The amorphous polyester resin of the present invention, the crystalline polyester resin, the Tg of the release agent, the acid value, the hydroxyl value, and the molecular weight may be measured as toner raw materials, respectively. It is possible to calculate the Tg, the molecular weight, and the weight ratio of the constituent components by performing the analysis method described later for each separated component.
That is, 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 integral of the elution curve are collected.
After concentrating and drying this collected eluate with an evaporator or the like, the solid content is dissolved in a heavy solvent such as deuterated chloroform or deuterated THF, and 1H-NMR measurement is performed. From the integration ratio of each element, The constituent monomer ratio 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.

<< Component Analysis of Toner >>
An example of a separation unit for each component when analyzing the toner will be described.
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 at every predetermined count. 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 occupies 90% or more is defined as the resin B, and the extract recovered in the fraction in which the crystalline polyester resin occupies 90% or more is the crystalline polyester resin. As described above, the extract recovered in the fraction occupying 90% or more of the release agent can be treated as the release agent.

  As an example of a means for measuring the content of the sulfo-substituted benzenedicarboxylic acid metal salt unit in the toner, for example, 100 mg of the THF soluble part of the toner is added with 4 mL of DMSO, 1 mL of 5N NaOH methanol solution, and stirred at 120 ° C. for 10 minutes. The obtained solution was analyzed by HPLC, and a method for qualitatively and quantitatively determining the sulfo-substituted benzene dicarboxylic acid metal salt from the obtained spectrum, and the content of the sulfo-substituted benzene dicarboxylic acid metal salt unit in the THF-soluble component was determined by LC / A method for quantification by MS is mentioned. The content of the unit in the toner is obtained from the unit content in the toner THF-soluble matter obtained from the HPLC and LC / MS and the THF-insoluble content such as a pigment and an external additive.

<< Measurement Method of Acid Value and Hydroxyl Value >>
The hydroxyl value can be measured using a method based on JIS K0070-1966.
Specifically, first, 0.5 g of a sample is precisely weighed into a 100 mL volumetric flask, and 5 mL of an acetylating reagent is added thereto. Next, after heating in a 100 ± 5 ° C. warm bath for 1 to 2 hours, the flask is removed from the warm bath and allowed to cool. Furthermore, acetic anhydride is decomposed by adding water and shaking. Next, in order to completely decompose acetic anhydride, the flask is again heated in a warm bath for 10 minutes or more and allowed to cool, and then the wall of the flask is thoroughly washed with an organic solvent.
Furthermore, the hydroxyl value was measured at 23 ° C. using an automatic potentiometric titrator DL-53 Titrator (manufactured by METTLER TOLEDO) and electrode DG113-SC (manufactured by METTLER TOLEDO), and analysis software LabX Light Version 1.00 Analyze using .000. For calibration of the apparatus, a mixed solvent of 120 mL of toluene and 30 mL of ethanol is used.
At this time, the measurement conditions are as follows.

〔Measurement condition〕
Stir
Speed [%] 25
Time [s] 15
EQP titration
Titrant / Sensor
Titrant CH ₃ ONa
Concentration [mol / L] 0.1
Sensor DG115
Unit of measurement mV
Predispensing to volume
Volume [mL] 1.0
Wait time [s] 0
Titrant addition Dynamic
dE (set) [mV] 8.0
dV (min) [mL] 0.03
dV (max) [mL] 0.5
Measure mode Equilibrium controlled
dE [mV] 0.5
dt [s] 1.0
t (min) [s] 2.0
t (max) [s] 20.0
Recognition
Threshold 100.0
Steepest jump only No
Range No
Tendency None
Termination
at maximum volume [mL] 10.0
at potential No
at slope No
after number EQPs Yes
n = 1
comb.termination conditions No
Evaluation
Procedure Standard
Potential1 No
Potential2 No
Stop for reevaluation No

The acid value can be measured using a method based on JIS K0070-1992.
Specifically, first, 0.5 g of a sample (0.3 g in the case of an ethyl acetate-soluble component) is added to 120 mL of toluene and dissolved by stirring at 23 ° C. for about 10 hours. Next, 30 mL of ethanol is added to prepare a sample solution. When the sample does not dissolve, a solvent such as dioxane or tetrahydrofuran is used. Furthermore, an acid value was measured at 23 ° C. using an automatic potentiometric titrator DL-53 Titator (manufactured by METTLER TOLEDO) and electrode DG113-SC (manufactured by METTLER TOLEDO), and analysis software LabX Light Version 1.00 Analyze using .000. For calibration of the apparatus, a mixed solvent of 120 mL of toluene and 30 mL of ethanol is used.
At this time, the measurement conditions are the same as in the case of the hydroxyl value described above.

  The acid value can be measured as described above. Specifically, titration is performed with a 0.1N potassium hydroxide / alcohol solution standardized in advance, and the acid value [mg KOH / g] = The acid value is calculated by titration [mL] × N × 56.1 [mg / mL] / sample weight [g] (where N is a factor of 0.1 N potassium hydroxide / alcohol solution).

<< 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 instrument). 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.
Moreover, when there is no notice in particular about the glass transition temperature and melting | fusing point of other structural components, such as an amorphous polyester, crystalline polyester, a mold release agent, the endothermic peak top at the time of the 2nd temperature rise, Tg is melting | fusing point of each object sample, Tg.

<< Measurement Method of Particle Size Distribution >>
The volume average particle diameter (D ₄ ) and the number average particle diameter (D _n ) of the toner, and the ratio (D ₄ / D _n ) thereof are, for example, Coulter Counter TA-II, Coulter Multisizer II (both manufactured by Coulter Inc.) ) And the like. 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 (D ₄ ) and the number average particle diameter (D _n ) 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 peak molecular weight 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: THF
Flow rate: 0.35 ml / min
Sample: Pretreatment of 0.15% sample injected into 0.4 ml sample: Toner was dissolved in tetrahydrofuran THF (made by Wako Pure Chemical Industries, Ltd.) at 0.15 wt% and filtered through a 0.2 μm filter. 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 a standard polystyrene sample for preparing a calibration curve, Showd STANDARD Std. No S-7300, S-210, S-390, S-875, S-1980, S-10.9, S-629, S-3.0, S-0.580, and toluene were used. An RI (refractive index) detector was used as the detector.

<Toner production method>
[Toner Production Method]
In the toner manufacturing method of the present invention, the toner manufacturing method is not particularly limited and may be appropriately selected depending on the intended purpose. At least the amorphous polyester resin, the crystalline polyester resin, A solution or dispersion formed by dissolving or dispersing a toner material mainly composed of a release agent and a colorant in an organic solvent is emulsified or dispersed in an aqueous medium containing styrene / acrylic resin fine particles and acrylic resin fine particles. Disperse to prepare an emulsified or dispersed liquid, granulate, adhere the acrylic resin fine particles to the toner precursor containing the emulsified or dispersed toner material, remove the organic solvent, and form the toner particles. It is preferable to produce a desired toner by heat-treating water containing water. 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 the active hydrogen group is contained in the aqueous medium. Toner precursor particles including an adhesive base material obtained by reacting a containing compound and a polymer capable of reacting with an active hydrogen group-containing compound are produced, and a desired toner is produced by attaching acrylic resin fine particles.

(Dissolution or dispersion of toner material)
The solution or dispersion of the toner material is prepared by dissolving or dispersing the toner material in a solvent.
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, it can react with an amorphous resin, an active hydrogen group-containing compound, or the active hydrogen group-containing compound. A polymer (prepolymer) and a colorant, and may contain other components such as a mold release agent and 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 crosslinking 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 stirring, or appropriately while checking 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 include an active hydrogen group-containing compound and a polymer having a site capable of reacting with the active hydrogen group-containing compound. Depending on the combination, it can be appropriately selected.
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. 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 less than 50 parts by mass, the dispersion state of the toner material is deteriorated, and toner mother particles having a predetermined particle size may not be obtained, and the amount exceeds 2,000 parts by mass. The production cost may increase.

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.
The catalyst is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include dibutyltin laurate and dioctyltin laurate.

(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 may be appropriately selected depending on the purpose. 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 carrier scattering. When the volume average particle diameter is more than 150 μm, the specific surface area is decreased, and the toner In the case of a full color with many solid portions, reproduction of the solid portions may be deteriorated.

<Preparation of toner>
[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] was 418.

[Synthesis of Amorphous 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, 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, the intermediate polyester and isophorone diisocyanate were charged at a molar ratio of 2.0 in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, diluted to 50% with ethyl acetate, and then 100 ° C. For 5 hours to obtain a prepolymer A-1.

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 resin A-1. Table 1 shows the physical property values of the obtained resin A-1.

[Synthesis of Amorphous Resin A-2]
1,6-hexanediol, isophthalic acid, adipic acid, trimellitic anhydride and OH / COOH which is the molar ratio of hydroxyl group to carboxyl group is 1 The diol component is 100 mol% of 1,6-hexanediol, the dicarboxylic acid component is 80 mol% of isophthalic acid, 20 mol% of adipic acid, and the amount of trimellitic anhydride in all monomers is 1 mol%. In the same manner, it was charged together with titanium tetraisopropoxide (1000 ppm vs. resin component). Thereafter, the temperature was raised to 200 ° C. in about 4 hours, 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, the intermediate polyester and isophorone diisocyanate were charged at a molar ratio of 2.0 in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, diluted to 50% with ethyl acetate, and then 100 ° C. For 5 hours to obtain prepolymer A-2.

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 resin A-2. Table 1 shows the physical property values of the obtained resin A-2.

[Synthesis of Amorphous Resin A-3]
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction pipe, OH / COOH, which is a molar ratio of hydroxyl group to carboxyl group, is added to 3-methyl-1,5-pentanediol, adipic acid, and trimellitic anhydride. 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 100 mol% of adipic acid, and the amount of trimellitic anhydride in all monomers is 1 mol%. In the same manner, it was charged together with titanium tetraisopropoxide (1000 ppm vs. resin component). Thereafter, the temperature was raised to 200 ° C. in about 4 hours, 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, the intermediate polyester and isophorone diisocyanate were charged at a molar ratio of 2.0 in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, diluted to 50% with ethyl acetate, and then 100 ° C. For 5 hours to obtain Prepolymer A-3.

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 resin A-3. Table 1 shows the physical property values of the obtained resin A-3.

[Synthesis of Amorphous Resin A-4]
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, OH / COOH, which is a molar ratio of hydroxyl group to carboxyl group, is added to 3-methyl-1,5-pentanediol, isophthalic acid, and trimellitic anhydride. 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 100 mol% of isophthalic acid, and the amount of trimellitic anhydride in all monomers is 1 mol%. In the same manner, it was charged together with titanium tetraisopropoxide (1000 ppm vs. resin component). Thereafter, the temperature was raised to 200 ° C. in about 4 hours, 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, the intermediate polyester and isophorone diisocyanate were charged at a molar ratio of 2.0 in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, diluted to 50% with ethyl acetate, and then 100 ° C. For 5 hours to obtain prepolymer A-4.

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 resin A-4. Table 1 shows the physical properties of the obtained resin A-4.

[Synthesis of Amorphous Resin A-5]
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction pipe, 3-methyl-1,5-pentanediol, decanedioic acid, trimellitic anhydride is a molar ratio of hydroxyl group to carboxyl group, OH / COOH 1.5, the diol component is 100 mol% 3-methyl-1,5-pentanediol, the dicarboxylic acid component is 100 mol% decanedioic acid, and the amount of trimellitic anhydride in all monomers is 1 mol% So that titanium tetraisopropoxide (1000 ppm vs. resin component) was added. Thereafter, the temperature was raised to 200 ° C. in about 4 hours, 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, the intermediate polyester and isophorone diisocyanate were charged at a molar ratio of 2.0 in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, diluted to 50% with ethyl acetate, and then 100 ° C. For 5 hours to obtain Prepolymer A-5.

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 resin A-5. Table 1 shows the physical properties of the obtained resin A-5.

[Synthesis of Amorphous Resin B-1]
In a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, the molar ratio of bisphenol A ethylene oxide side 2 mol adduct / bisphenol A propylene oxide 2 mol adduct is 85/15. -Sodium sulfoisophthalate, isophthalic acid, and adipic acid in a molar ratio of 2/78/20, OH / COOH, which is the molar ratio of hydroxyl group to carboxyl group, is charged in 1.3, and is usually added together with 500 ppm of titanium tetraisopropoxide. The reaction was carried out at 230 ° C. for 8 hours, and after further reaction for 4 hours at a reduced pressure of 10 mmHg to 15 mmHg. Reaction was performed for a time to obtain amorphous resin B-1. The characteristic values are shown in Table 1.

[Synthesis of Amorphous Resin B-2]
In a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, the molar ratio of bisphenol A ethylene oxide side 2 mol adduct / bisphenol A propylene oxide 2 mol adduct is 85/15. -Sodium sulfoisophthalate, isophthalic acid, and adipic acid in a molar ratio of 0.3 / 79.7 / 20, OH / COOH, which is the molar ratio of hydroxyl group to carboxyl group, was charged in 1.3, and 500 ppm of titanium tetraiso After reacting at 230 ° C. for 8 hours at normal pressure with propoxide, and further reacting for 4 hours at a reduced pressure of 10 mmHg to 15 mmHg, trimellitic anhydride was added to the reaction vessel so as to be 1 mol% based on the total resin components, 180 ° C., Reaction was performed at normal pressure for 3 hours to obtain amorphous resin B-2. The characteristic values are shown in Table 1.

[Synthesis of Amorphous Resin B-3]
In a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, the molar ratio of bisphenol A ethylene oxide side 2 mol adduct / bisphenol A propylene oxide 2 mol adduct is 85/15. -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, is charged in 1.3, and is usually used together with 500 ppm of titanium tetraisopropoxide. The reaction was carried out at 230 ° C. for 8 hours, and after further reaction for 4 hours at a reduced pressure of 10 mmHg to 15 mmHg. Reaction was performed for a time to obtain amorphous resin B-3. The characteristic values are shown in Table 1.

[Synthesis of Amorphous 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 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 atmospheric pressure for 3 hours Reaction was performed to obtain amorphous resin B-4. The characteristic values are shown in Table 1.

[Synthesis of Amorphous Resin B-5]
A four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was adjusted to 85/15 in terms of a molar ratio of bisphenol A ethylene oxide side 2 mol adduct / bisphenol A propylene oxide 2 mol adduct. -Sodium sulfoterephthalate, isophthalic acid, and adipic acid in a molar ratio of 2/78/20, OH / COOH, which is the molar ratio of hydroxyl group to carboxyl group, is charged in 1.3, and is usually used together with 500 ppm of titanium tetraisopropoxide. The reaction was carried out at 230 ° C. for 8 hours, and after further reaction for 4 hours at a reduced pressure of 10 mmHg to 15 mmHg. Reaction was performed for a time to obtain amorphous resin B-5. The characteristic values are shown in Table 1.

[Synthesis of amorphous resin B-6]
In a four-necked flask equipped with a nitrogen inlet tube, a dehydrating tube, a stirrer, and a thermocouple, the molar ratio of bisphenol A ethylene oxide side 2 mol adduct / bisphenol A propylene oxide 2 mol adduct is 85/15. -Sodium sulfophthalate, isophthalic acid, and adipic acid in a molar ratio of 2/78/20, 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. Reaction was performed to obtain amorphous resin B-6. The characteristic values are shown in Table 1.

[Synthesis of Amorphous Resin B-7]
In a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, the molar ratio of bisphenol A ethylene oxide side 2 mol adduct / bisphenol A propylene oxide 2 mol adduct is 85/15. -Lithium sulfoisophthalate, isophthalic acid, and adipic acid in a molar ratio of 2/78/20, OH / COOH, which is the molar ratio of hydroxyl group to carboxyl group, is charged in 1.3, and is usually used together with 500 ppm of titanium tetraisopropoxide. The reaction was carried out at 230 ° C. for 8 hours, and after further reaction for 4 hours at a reduced pressure of 10 mmHg to 15 mmHg. Reaction was performed for a time to obtain amorphous resin B-7. The characteristic values are shown in Table 1.

[Synthesis of Amorphous Resin B-8]
In a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, the molar ratio of bisphenol A ethylene oxide side 2 mol adduct / bisphenol A propylene oxide 2 mol adduct is 85/15. -Potassium sulfoisophthalate, isophthalic acid, and adipic acid in a molar ratio of 2/78/20, OH / COOH, which is the molar ratio of hydroxyl group to carboxyl group, is charged in 1.3, and is usually used together with 500 ppm of titanium tetraisopropoxide. The reaction was carried out at 230 ° C. for 8 hours, and after further reaction for 4 hours at a reduced pressure of 10 mmHg to 15 mmHg. The reaction was continued for a while to obtain amorphous resin B-8. The characteristic values are shown in Table 1.

[Synthesis of Amorphous Resin B-9]
A four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple is mixed with bisphenol A ethylene oxide side 2 mol adduct / bisphenol A propylene oxide 2 mol adduct at a molar ratio of 85/15. Acid / Adipic acid was adjusted to 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. for 8 hours at normal pressure. 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 the total resin components, and reacted at 180 ° C. and normal pressure for 3 hours. -9 was obtained. The characteristic values are shown in Table 1.

[Synthesis of Amorphous Resin B-10]
In a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, the molar ratio of bisphenol A ethylene oxide side 2 mol adduct / bisphenol A propylene oxide 2 mol adduct is 85/15. -Sodium sulfoisophthalate, isophthalic acid, and adipic acid in a molar ratio of 15/65/20, OH / COOH, which is the molar ratio of hydroxyl group to carboxyl group, is charged in 1.3, and is usually added together with 500 ppm of titanium tetraisopropoxide. The reaction was carried out at 230 ° C. for 8 hours, and after further reaction for 4 hours at a reduced pressure of 10 mmHg to 15 mmHg. Reaction was performed for a while to obtain an amorphous resin B-10. The characteristic values are shown in Table 1.

[Synthesis of Crystalline Resin C-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 dodecanoic acid 100 mol%, the component ratio of the alcohol component was 1,6-hexanediol 100 mol%, and after reacting with 500 ppm of titanium tetraisopropoxide at 180 ° C. for 10 hours, the temperature was raised to 200 ° C. and reacted for 3 hours, Furthermore, it was made to react at a pressure of 8.3 kPa for 2 hours to obtain a crystalline resin C-1. The characteristic values are shown in Table 1.

[Synthesis of Crystalline Resin C-2]
In a 5 L four-necked flask equipped with a nitrogen introduction tube, dehydration tube, stirrer and 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 adipic acid The composition ratio of the alcohol component is 100 mol%, 1,6-hexanediol 50 mol%, and 1-4 butanediol 50 mol%. After reacting with 500 ppm of titanium tetraisopropoxide at 180 ° C for 10 hours, the temperature rises to 200 ° C. The mixture was allowed to warm for 3 hours and further reacted at a pressure of 8.3 kPa for 2 hours to obtain crystalline resin C-2. The characteristic values are shown in Table 1.

[Synthesis of Crystalline Resin C-3]
In a 5 L four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer and 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 terephthalic acid The composition ratio of the alcohol component is 100 mol%, 1,6-hexanediol 50 mol%, and 1-4 butanediol 50 mol%. After reacting with 500 ppm of titanium tetraisopropoxide at 180 ° C for 10 hours, the temperature rises to 200 ° C. The mixture was heated and reacted for 3 hours, and further reacted at a pressure of 8.3 kPa for 2 hours to obtain a crystalline resin C-3. The characteristic values are shown in Table 1.

[Example 1: Production 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 B-1 are added and mixed with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.), and the mixture is used with two rolls. After kneading at 150 ° C. for 30 minutes, the mixture was cooled and rolled and pulverized with a pulverizer to obtain [Master batch 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. at 1 hour, and the liquid feeding speed was measured using a bead mill (Ultra Visco Mill, manufactured by IMEX). Dispersion was performed under the conditions of 1 kg / hr, disk peripheral speed of 6 m / second, 0.5 mm zirconia beads at 80% by volume, and 3 passes to obtain [WAX dispersion].

(Preparation of crystalline polyester dispersion 1)
In a container equipped with a stirrer and a thermometer, 50 parts of crystalline resin C-1 and 450 parts of ethyl acetate were charged, heated to 80 ° C. with stirring, held at 80 ° C. for 5 hours, and then at 1 hour. Cooled to 30 ° C., using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), liquid feeding speed 1 kg / hr, disk peripheral speed 6 m / second, 80% by volume of 0.5 mm zirconia beads, 3 pass conditions To obtain a [crystalline polyester dispersion].

(Preparation of oil phase)
[WAX dispersion] 500 parts, [Prepolymer A-1] 300 parts, [Crystalline resin dispersion 1] 500 parts, [Amorphous resin B-1] 650 parts, [Masterbatch 1] 100 parts and Two parts of ketimine compound 1] were put in a container and mixed for 60 minutes at 5,000 rpm with a TK homomixer (made by Tokushu Kika) to obtain [Oil Phase 1].
The weight ratio of each component is shown in Table 2.

(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 were mixed and stirred, and 50 parts by weight 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 13,000 rpm for 20 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 operation of (1) to (5) 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].
[Filtration cake 1] was dried at 45 ° C. for 48 hours with a circulating dryer, and sieved with a mesh of 75 μm to obtain [Toner 1].

[Example 2: Production of toner 2]
[Toner 2] of Example 2 was obtained in the same manner except that the amorphous resin B-1 of Example 1 was changed to amorphous resin B-2.

[Example 3: Production of toner 3]
[Toner 3] of Example 3 was obtained in the same manner except that the amorphous resin B-1 of Example 1 was changed to amorphous resin B-3.

[Example 4: Production of toner 4]
[Toner 4] of Example 4 was obtained in the same manner except that the amorphous resin B-1 of Example 1 was changed to amorphous resin B-4.

[Example 5: Production of toner 5]
[Toner 5] of Example 5 was obtained in the same manner except that Prepolymer A-1 of Example 1 was changed to Prepolymer A-2.

[Example 6: Production of toner 6]
[Toner 6] of Example 6 was obtained in the same manner except that Prepolymer A-1 of Example 1 was changed to Prepolymer A-3.

[Example 7: Production of toner 7]
[Toner 7] of Example 7 was obtained in the same manner except that the crystalline C-1 of Example 1 was changed to crystalline C-2.

[Example 8: Production of toner 8]
[Toner 8] of Example 8 was obtained in the same manner except that the crystalline resin C-1 of Example 1 was changed to the crystalline resin C-3.

[Example 9: Production of toner 9]
In the preparation of the oil phase of Example 1, the same procedure was repeated except that 500 parts of [Prepolymer A-1], 1000 parts of [Crystalline polyester resin dispersion 1] and 500 parts of [Amorphous resin B-1] were used. Thus, [Toner 9] of Example 9 was obtained.

[Example 10: Production of toner 10]
[Toner 10] of Example 10 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 140 parts and [Amorphous resin B-1] was changed to 730 parts. .

[Example 11: Production of toner 11]
[Toner 11] of Example 11 was obtained in the same manner except that the amorphous resin B-1 of Example 1 was changed to amorphous resin B-5.

[Example 12: Production of toner 12]
[Toner 12] of Example 12 was obtained in the same manner except that the amorphous resin B-1 of Example 1 was changed to amorphous resin B-6.

[Example 13: Production of toner 13]
[Toner 13] of Example 13 was obtained in the same manner except that the amorphous resin B-1 of Example 1 was changed to amorphous resin B-7.

[Example 14: Production of toner 14]
[Toner 14] of Example 14 was obtained in the same manner except that the amorphous resin B-1 of Example 1 was changed to amorphous resin B-8.

[Comparative Example 1: Production of Toner 15]
[Toner 15] of Comparative Example 1 was obtained in the same manner except that the amorphous resin B-1 of Example 1 was changed to amorphous resin B-9.

[Comparative Example 2: Production of Toner 16]
[Toner 16] of Comparative Example 2 was obtained in the same manner except that the amorphous resin B-1 of Example 1 was changed to amorphous resin B-10.

[Comparative Example 3: Production of Toner 17]
[Toner 17] of Comparative Example 3 was obtained in the same manner except that Prepolymer A-1 of Example 1 was changed to Prepolymer A-4.

[Comparative Example 4: Production of Toner 18]
[Toner 18] of Comparative Example 4 was obtained in the same manner except that Prepolymer A-1 of Example 1 was changed to Prepolymer A-5.

[Comparative Example 5: Production of toner 19]
In the preparation of the oil phase in Example 1, [Prepolymer A-1] was changed to 600 parts, [Crystalline Polyester Resin Dispersion Solution 1] 1000 parts, and [Amorphous B-1] 450 parts. [Toner 19] of Comparative Example 5 was obtained.

[Comparative Example 6: Production of toner 20]
[Toner 20] of Comparative Example 6 was obtained in the same manner except that 60 parts of [Prepolymer A-1] and [Amorphous resin B-1] were changed to 770 parts in the preparation of the oil phase of Example 1. .

[Comparative Example 7: Production of toner 21]
[Toner 21] of Comparative Example 7 was obtained in the same manner as in the preparation of the oil phase of Example 1, except that [crystalline polyester resin dispersion 1] was changed to 0 part.

[Comparative Example 8: Production of toner 22]
[Toner 22] of Comparative Example 8 was obtained in the same manner except that the acrylic resin fine particles a of Example 1 were changed to 0 parts by weight.

<Evaluation>
A developer was prepared for the obtained toner by the following method, and the following evaluation was performed. The results are shown in Table 3.
<< Preparation of 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.
-Production of developer-
Using a ball mill, 15 parts of the toner and 95 parts of the carrier were mixed to prepare a developer.

<< Low-temperature fixability and high-temperature offset resistance >>
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 used.
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.

<< 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.
◎: 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

<< Filming >>
The image forming apparatus MF2800 (manufactured by Ricoh Co., Ltd.) was used to visually inspect the photoconductor after 10,000 images were formed, and the toner component, mainly the release agent, was fixed to the photoconductor. It was evaluated according to the following evaluation criteria.
A: The toner component is not fixed to the photoconductor. A: The toner component is fixed to the photoconductor. However, this is not a practical problem. Δ: The toner component is fixed to the photoconductor. , Is a level that causes a problem in practical use. ×: The toner component can be firmly fixed to the photosensitive member, and is a level having a large problem in practical use.

≪Pigment dispersibility≫
After embedding the toner in a 30 minute curing type two-component mixed epoxy resin and curing for 24 hours, the epoxy resin embedding the toner was cut to a thickness of about 0.5 μm using an ultramicrotome, and the cross section of the toner was Observed with an optical microscope, the pigment dispersion state inside the toner was evaluated according to the following criteria.
○: Pigment particles are uniformly dispersed inside the toner.
Δ: Some pigments are unevenly distributed near the surface of the toner, but this is not a practically problematic level.
X: Most pigments are unevenly distributed in the vicinity of the surface of the toner, and are practically problematic.

Japanese Patent Laid-Open No. 11-133665 JP 2001-66827 A Japanese Patent No. 3661422 JP 2009-169383 A JP 2010-54669 A

Claims (11)

  In a toner containing at least a colorant, a binder resin, and a release agent, the binder resin is composed of at least two types of amorphous resins A and B and a crystalline resin, and the amorphous resin A has a glass transition. The resin is a resin having a temperature of −60 ° C. or more and less than 0 ° C., having a branched structure and having a urethane or urea bond, and the amorphous resin B has a glass transition temperature of 40 ° C. or more and less than 70 ° C. And a unit obtained from any one of sulfo-substituted benzenedicarboxylic acid metal salts and their esters, and the content of the unit in the toner is 0.05% to 4% by weight. .   The toner according to claim 1, wherein the amorphous resins A and B and the crystalline resin are amorphous polyester resins A and B and a crystalline polyester resin, respectively.   The content of a unit obtained from any one of the sulfo-substituted benzenedicarboxylic acid metal salt and the ester in the resin B is 0.1 wt% to 5 wt%. The toner described.   The toner according to claim 1, wherein the sulfo-substituted benzenedicarboxylic acid metal salt and an ester thereof are sodium salts.   The toner according to claim 1, wherein the sulfo-substituted benzenedicarboxylic acid metal salt is sodium 5-sulfoisophthalate.   The toner according to claim 1, wherein the content of the resin B in the toner is 50 wt% or more and less than 90 wt%.   The toner according to claim 1, wherein the content of the resin A in the toner is 5 wt% or more and less than 25 wt%.   The toner according to claim 1, wherein the crystalline polyester includes a crystalline polyester having a melting point of 60 ° C. or higher and lower than 80 ° C., and Tg1st-Tg2nd of the toner is 10 ° C. or higher.   The toner particles of the toner are composed of core particles composed of a colorant, a binder resin, and a release agent, and a resin layer formed on the outside of the core particles, and the resin layer is a layer I composed of at least styrene / acrylic resin fine particles; The toner according to claim 1, further comprising a layer E composed of acrylic resin fine particles.   The toner according to claim 1, further comprising a release agent having a melting point of 50 ° C. or higher and lower than 90 ° C.   An image forming developer comprising the toner according to claim 1.