JP2013190720A - Toner for image formation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner that has excellent low-temperature releasability, suppresses the occurrence of filming, achieves both low-temperature fixability and heat-resistance storability, provides high image quality even after a long period of use, and has a small particle diameter and a narrow particle size distribution, and a manufacturing method of the toner; developer using the toner; a container having toner therein; an image forming method; a process cartridge; and an image forming apparatus.SOLUTION: A toner contains at least a binder resin, colorant, and a mold release agent, and toner particles have a core/shell structure. The shell includes a layer A comprising styrene-acrylic resin fine particles, and a layer B and a layer C comprising acrylic resin fine particles; and the shell layer A is provided outside the shell layer B, and the shell layer C is provided on an outermost surface.

Description

  The present invention relates to a toner, a toner manufacturing method, a developer using the toner, a toner-containing container, an image forming method, a process cartridge, and an image forming apparatus.

In recent years, the market demanded smaller particle size for higher image quality and low-temperature fixing for energy saving. In particular, image formation is possible after the image forming apparatus is ready for energy saving. In order to reduce as much as possible the amount of power required for the waiting time (warm-up time of the apparatus) until the time is reached, there is a strong demand for shortening the waiting time. However, the toner obtained by the usual kneading and pulverization method is approaching the limit of reducing the particle size technically, its shape is irregular, the particle size distribution is broad, and the fixing energy is high. was there.
In particular, in the fixing, the kneaded and pulverized toner prepared by the pulverization method is cracked at the interface of the release agent (wax), so that a lot of the release agent is present on the toner surface, so that the release effect is easily produced. The toner easily adheres to the carrier, the photoreceptor, and the blade, and the performance is unsatisfactory.

In order to overcome the problems associated with the kneading and pulverizing method, a toner manufacturing method using a polymerization method has been proposed. In this polymerization method, it is easy to reduce the particle size of the toner, and the particle size distribution is sharper than the particle size distribution of the toner by the pulverization method, and it is possible to encapsulate wax.
For example, the proposal about the emulsion polymerization aggregation method is made | formed (refer patent document 1 and 2). There has also been proposed a technique for improving the problems in the use of the surfactant possessed by the emulsion aggregation method (see Patent Documents 3 and 4).

  In addition, for the purpose of improving toner fluidity, low-temperature fixability, and hot offset property, a practical sphericity of 0.90 to 1.00 using a urethane-modified polyester extension reaction product as a toner binder is used. A dry toner has been proposed (see Patent Document 5). In addition, a dry toner having excellent powder flowability and transferability in the case of a small particle size toner and excellent in all of heat storage stability, low-temperature fixability, and hot offset resistance has been proposed ( (See Patent Documents 6 and 7).

An object of the present invention is to solve the conventional problems and achieve the following objects.
That is, the present invention is excellent in releasability at low temperature, has little filming, achieves both low-temperature fixability and heat-resistant storage stability, and obtains high image quality even in long-term use. It is an object of the present invention to provide a narrow toner and a toner production method, a developer using the toner, a toner-containing container, an image forming method, a process cartridge, and an image forming apparatus.

Means for solving the above-described problems are as follows. That is,
(1) Toner particles having at least a binder resin, a colorant, and a release agent and having a core / shell structure, wherein the shell includes a layer A composed of styrene / acrylic resin fine particles and a layer B composed of acrylic resin fine particles. A toner comprising the shell layer A on the outer side of the shell layer B, and the shell layer C on the outermost surface.
(2) The toner as described in (1) above, wherein the glass transition temperature in the first temperature increase is higher than 20 ° C. and lower than 40 ° C.
(3) The toner according to (1) or (2), wherein Tg1st-Tg2nd is 10 ° C. or higher.
(4) The toner according to any one of (1) to (3), wherein the core further contains a crystalline resin.
(5) The resin fine particles for the resin fine particle layer A are fine particles of a crosslinked resin containing at least one of a styrene polymer, an acrylate polymer, and a methacrylic acid ester polymer, and a glass transition temperature is The toner according to any one of Items (1) to (4), which is higher than 40 ° C. and lower than 200 ° C.
(6) The resin fine particle layer B is fine particles of a crosslinked resin containing at least one of an acrylate polymer and a methacrylic ester polymer, and the glass transition temperature is higher than 50 ° C. and lower than 110 ° C. The toner according to any one of items (1) to (5).
(7) Items (1) to (6), wherein the resin fine particle layer C is fine particles of a crosslinked resin containing at least one of an acrylate polymer and a methacrylate polymer. The toner according to any one of the above.
(8) The binder resin comprises two kinds of amorphous polyester, and one resin D of the amorphous polyester has a glass transition temperature of −60 ° C. or higher and lower than 0 ° C. and has a branched structure. The polyester having a functional group capable of being bonded with urea or urethane is modified, and the other resin E of the amorphous polyester is an unmodified polyester having a glass transition temperature of more than 40 ° C. and less than 70 ° C. The toner according to any one of (1) to (7).
(9) The toner according to any one of (1) to (8) above, which is produced by granulation in an aqueous medium.
(10) An electrostatic latent image developer comprising the toner according to any one of (1) to (8) and a carrier.
(11) An electrostatic latent image carrier, charging means for charging the surface of the electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, Developing means for developing the latent image with the toner according to any one of (1) to (8), and transfer means for transferring the toner image to an image bearing medium; An image forming apparatus comprising fixing means for fixing a toner image on an image bearing medium.

  As will be understood from the following detailed and specific description, according to the present invention, the above-described problems can be solved, the object can be achieved, the mold release property at low temperature is excellent, and the filming , A toner having a small particle size and a narrow particle size distribution, and a developer using the toner, in which low-temperature fixability and heat-resistant storage stability are both achieved, and high image quality can be obtained even after long-term use. In addition, the toner container, the image forming method, the process cartridge, and the image forming apparatus can be provided.

[toner]
The present invention will be described in detail below. The toner for developing an electrostatic image of the present invention (hereinafter sometimes simply referred to as “toner”) is a toner particle having a core / shell structure containing at least two kinds of amorphous polyester resin and crystalline polyester. The shell includes a layer A made of styrene / acrylic resin fine particles, B and C made of acrylic resin fine particles, a shell layer B made of acrylic resin fine particles inside the shell layer A, and a shell layer outside C is provided.
The film thickness of the resin fine particle layer A is more than 10 nm and less than 100 nm, the film thickness of the resin fine particle B is more than 10 nm and less than 100 nm, and the T1 / 2 temperature of the styrene / acryl resin fine particles is over 140 ° C. and 200 It is preferable that the T1 / 2 temperature of the acrylic resin fine particles is higher than 110 ° C and lower than 180 ° C.
Hereinafter, the toner of the present invention will be described in detail.

  In the toner of the present invention, a coating layer in which resin fine particles B are adhered is formed on the surface of a toner particle main body having a toner material mainly including a colorant and a binder resin, and further, resin fine particles are formed outside the coating layer. A three-layer structure with A attached is formed. The average particle diameter of the toner is adjusted by, for example, emulsification or dispersion conditions such as stirring of the aqueous medium in the step of emulsifying the organic solvent containing the toner material in the aqueous medium.

In recent years, polyesters for toner binders tend to be used in which the molecular weight is lowered and the melt viscosity is lowered due to a reduction in environmental load due to reduction of power consumption during fixing. However, in many cases, the glass transition temperature of the binder resin and the toner is 40 ° C. to 60 ° C. from the viewpoint of storage stability of the toner. In these cases, although the storage stability of the toner is ensured, it is difficult to reduce the melt viscosity of the toner to a level at which sufficient low-temperature fixability is expressed.
The present invention is preferably a toner of toner particles having a core / shell structure containing at least two kinds of amorphous polyester resins (polyester D, polyester E) and crystalline polyester, wherein the polyester D content is 1 A layer composed of styrene / acrylic resin fine particles and B composed of acrylic resin fine particles, and a layer composed of acrylic resin fine particles outside the shell layers A and B. C is provided. The resin fine particle layer A has a thickness of more than 10 nm and less than 100 nm, the resin fine particle B has a thickness of more than 10 nm and less than 100 nm, and the styrene / acrylic resin fine particles (hereinafter referred to as “ The T1 / 2 temperature of the styrene / acrylic resin fine particles A ”or simply“ resin fine particles A ”is more than 140 ° C. and less than 200 ° C., and the acrylic resin fine particles for the layer B (hereinafter referred to as“ acrylic ”). The toner is characterized in that the T1 / 2 temperature of “resin fine particles B” or simply “resin fine particles B” is more than 110 ° C. and less than 180 ° C. Two types of amorphous polyester resins D and E and crystalline polyester are used for the core of the toner particles, and by lowering the glass transition temperature of the toner, the melt viscosity of the whole toner is lowered and low temperature fixability is expressed. The inventors have found that the storage stability can be ensured without hindering the low-temperature fixability of the toner by the two coating layers having a constant film thickness formed outside the toner base particles.

The toner for forming an electrostatic image of the present invention preferably contains at least two kinds of polyester resins D and E as binder resins. In particular, the at least two kinds of polyester resins include a non-linear non-crystalline polyester resin D and a linear non-crystalline polyester resin E. It is preferable that the non-linear non-crystalline polyester resin D and the non-linear non-crystalline polyester resin E are completely compatible.
It is preferable to include the non-linear reactive polyester resin D because the design of the molecular weight and the design of the thermal characteristics of the resin are expanded. In addition, by containing polyester resin D having a glass transition point in the ultra-low temperature range and high melt viscosity, the softening point of the resin as a whole is shifted to the low temperature side, but storage stability that does not easily deform and low temperature It is possible to achieve both fixing properties. In other words, it has a glass transition temperature in the ultra-low temperature range, but by combining non-crystalline polyester resin D with high melt viscosity with other non-crystalline polyester resin E in a compatible state, low-temperature fixability and It is possible to achieve a trade-off between properties such as storage stability.

<Amorphous polyester D>
The other amorphous polyester resin D is composed of a non-linear reactive precursor a and a curing agent.
The reactive precursor a is a polyester having a reactive site such as isocyanate, epoxy, carbodiimide, etc. at the terminal, and is particularly preferably a terminal NCO compound of a polyester polyurethane.
As the polyhydric alcohol component in the polyester, any of the conventionally known polyhydric alcohol components may be used alone and / or mixed, but from the viewpoint of blocking resistance, image storage stability, and low-temperature fixability, 3-methyl- Aliphatic diols such as 1,5-pentanediol and neopentyl glycol are preferred. As the acid component, any conventionally known one can be used alone and / or mixed, but terephthalic acid, isophthalic acid, phthalic anhydride, adipic acid, sebacic acid, dodecanedicarboxylic acid and the like are preferable from the viewpoint of cost and the like. .

As the non-linear component, that is, a component for taking a branched structure, a conventionally known trifunctional or higher polyfunctional component can be used. However, from the viewpoint of cost and the like, trimethylolpropane is used for alcohols, and trimellitic anhydride is used for acids. Acid is preferred.
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.

A conventionally known amine compound can be suitably used as the curing agent.
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.].

<Amorphous polyester E>
The amorphous polyester E preferably has a Tg of more than 40 ° C. and less than 70 ° C. If the temperature is lower than 40 ° C., low-frequency fixability can be obtained, but the thermal characteristics as a toner are excessively lowered, which is not preferable because storage stability is deteriorated. When it exceeds 70 ° C., storage stability can be exhibited, but it is not preferable because the low-temperature fixability is deteriorated.

In the present invention, as the amorphous polyester resin E, an amorphous unmodified polyester resin is preferably used.
Examples of the alcohol component used in the amorphous polyester E include divalent alcohols (diols), specifically, alkylene glycols having 2 to 36 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3- Propylene glycol, 1,4-butylene glycol, 1,6-hexanediol, etc.); C4-C36 alkylene ether glycol (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, etc.) An alicyclic diol having 6 to 36 carbon atoms (such as 1,4-cyclohexanedimethanol and hydrogenated bisphenol A); an alkylene oxide having 2 to 4 carbon atoms of the alicyclic diol [ethylene oxide (hereinafter abbreviated as EO); ), Propylene oxide (hereinafter abbreviated as PO), butylene oxide (hereinafter abbreviated as BO), etc.] addition products (number of added moles 1-30); carbon of bisphenols (such as bisphenol A, bisphenol F and bisphenol S) Examples include adducts having 2 to 4 alkylene oxides (such as EO, PO, and BO) (addition moles of 2 to 30).

  Further, in addition to the above divalent diol, an alcohol component having 3 or more valences (3 to 8 valences or more) may be contained, specifically, 3 to 8 valences having 3 to 36 carbon atoms or more. The above aliphatic polyhydric alcohols (alkane polyols and intramolecular or intermolecular dehydrates such as glycerin, triethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, polyglycerin, and dipentaerythritol; Derivatives such as sucrose and methyl glucoside; etc.]; C 2-4 alkylene oxide (EO, PO, BO etc.) adducts of the above aliphatic polyhydric alcohols (addition moles 1-30); Trisphenols (Tris) C2-C4 alkylene oxide (EO, PO, BO, etc.) such as phenol PA Adduct (addition mole number 2-30); Novolak resin (phenol novolak, cresol novolak, etc .: average polymerization degree 3-60) C2-C4 alkylene oxide (EO, PO, BO etc.) addition product (addition mole) 2-30) etc. are mentioned.

  The carboxylic acid component used in the amorphous polyester E is a divalent carboxylic acid (dicarboxylic acid), specifically, an alkanedicarboxylic acid having 4 to 36 carbon atoms (succinic acid, apidic acid, sebacic acid, etc. ) And alkenyl succinic acid (such as dodecenyl succinic acid); alicyclic dicarboxylic acid having 4 to 36 carbon atoms (such as dimer acid (dimerized linoleic acid)); alkenedicarboxylic acid having 4 to 36 carbon atoms (maleic acid, fumaric acid, Citraconic acid, mesaconic acid, etc.); aromatic dicarboxylic acids having 8 to 36 carbon atoms (phthalic acid, isophthalic acid, terephthalic acid or derivatives thereof, naphthalenedicarboxylic acid, etc.). Of these, alkene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms are preferable. In addition, as a polycarboxylic acid, you may use the acid anhydride of the above-mentioned thing, or a lower alkyl (C1-C4) ester (Methyl ester, ethyl ester, isopropyl ester, etc.).

  Further, in addition to the above divalent carboxylic acid, it may contain a trivalent or higher (3 to 6 or higher) carboxylic acid component, specifically, an aromatic polycarboxylic acid having 9 to 20 carbon atoms. Acid (trimellitic acid, pyromellitic acid, etc.); vinyl polymer of unsaturated carboxylic acid [number average molecular weight (hereinafter referred to as “Mn”; measured by gel permeation chromatography (GPC)): 450 to 10,000] (Styrene / maleic acid copolymer, styrene / acrylic acid copolymer, α-olefin / maleic acid copolymer, styrene / fumaric acid copolymer, etc.). Among these, preferred are aromatic polycarboxylic acids having 9 to 20 carbon atoms, and particularly preferred are trimellitic acid and pyromellitic acid. In addition, as polycarboxylic acid more than trivalence, you may use the acid anhydride of the above-mentioned thing, or a lower alkyl (C1-C4) ester (Methyl ester, ethyl ester, isopropyl ester, etc.).

Therefore, a toner is produced using the non-linear amorphous polyester resin D having non-reactive ends and the linear amorphous polyester E as main binder resins.
As a toner production method, a kneading and pulverizing method is used in which a binder resin is melt-kneaded with a colorant and the like, then finely pulverized, and further classified. As a method for producing toner by granulating in a solvent such as an aqueous phase, there is a toner obtained by suspension polymerization method, emulsion polymerization aggregation method or the like. For example, in the suspension polymerization method, a monomer, a polymerization initiator, a colorant, a release agent, and the like are added to an aqueous phase containing a dispersion stabilizer while stirring to form oil droplets, and then heated to polymerize. In this method, toner particles are obtained by performing a reaction. The emulsion polymerization aggregation method uses, for example, a polyester resin as a binder resin, emulsified and dispersed in an aqueous phase, and then removed fine particles, a colorant, a release agent (wax) and the like. Toner particles are produced by agglomerating a dispersion formed by dispersing in an aqueous phase and heating and fusing. The toner of the present invention may be produced by any method by using this toner resin.

<Resin fine particles A>
The resin fine particle A is not particularly limited as long as it has a volume average particle diameter of 10 nm to 500 nm, and can be appropriately selected according to the purpose.
The resin for the resin fine particles A is not particularly limited, and a known resin can be appropriately selected according to the purpose, but is incompatible with the binder resin forming the toner base particles. preferable. Moreover, it is preferable that it is resin which can form an aqueous dispersion in an aqueous medium. Examples of the resin for the resin fine particles A include, for example, a styrene polymer, an acrylate polymer, a methacrylate polymer, a styrene-methyl acrylate copolymer, a styrene-ethyl acrylate copolymer, and styrene. -Butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethacrylate Examples include an acid methyl copolymer, a styrene-acrylonitrile copolymer, and a styrene-acrylonitrile-indene copolymer. Examples of the copolymer with styrene-other resins include styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene- Examples thereof include a vinyl methyl ketone copolymer, a styrene-butadiene copolymer, a styrene-isoprene copolymer, a styrene-maleic acid copolymer, and a styrene-maleic acid ester copolymer. Among these, a styrene polymer, an acrylic ester polymer, a methacrylic ester polymer, and a combination thereof are preferable.
The resin fine particles A are preferably fine particles of a crosslinked resin containing at least one of a styrene polymer, an acrylate polymer, and a methacrylic ester polymer.

  The volume average particle diameter of the resin fine particles A is 10 nm to 500 nm, and preferably 50 nm to 100 nm. When the volume average particle size is less than 10 nm, the spacer effect cannot be sufficiently obtained, so that the non-electrostatic adhesion force of the toner particles cannot be reduced. When the stress is large, the resin fine particles A and external additives are easily embedded in the toner surface, and there is a possibility that sufficient transfer efficiency cannot be maintained over a long period of time. When the volume average particle diameter exceeds 500 nm, the toner fluidity may be deteriorated or the coating layer may be thick, which may impair the low-temperature fixability of the toner.

The glass transition temperature (TgA) of the resin fine particles A is preferably 50 ° C. to 100 ° C., more preferably 65 ° C. to 85 ° C.
When the TgB is less than 50 ° C., sufficient heat storage stability in the storage temperature range of the toner cannot be obtained, and aggregation of the toner particles may occur. In some cases, the low-temperature fixability of the toner may be hindered.

  The addition amount of the resin fine particles A depends on the addition amounts of the remaining resin fine particles B and resin fine particles C, but is preferably 0.5% by mass to 5% by mass with respect to the toner, and 1% by mass to 4% by mass. Is more preferable. When the addition amount is less than 0.5% by mass, the non-electrostatic adhesion force of the toner particles may not be reduced because the spacer effect is not sufficiently obtained. There is a risk that the fluidity of the toner will deteriorate, the uniform transferability will be hindered, the fine particles will not be sufficiently fixed to the toner and will be easily detached, and will adhere to the carrier and the photoconductor, which will contaminate the photoconductor. is there.

In general, the toner filled in the developing machine is such that resin fine particles on the toner surface are embedded in the toner mainly due to mechanical stress inside the developing machine, or moved to the recesses on the surface of the toner particle main body, The effect of reducing adhesion is lost. Further, when the external additive is exposed to the same stress, it is buried inside the toner, and the adhesion force of the toner is increased.
However, the toner according to the production method of the present invention is deformed on the surface of the toner particles due to mechanical stress in the developing device because the resin fine particles A are relatively large and difficult to be embedded in the toner particle main body and are crosslinked and relatively hard. In addition, since the spacer effect is also maintained, the external additive is prevented from being buried, which is suitable for maintaining the above-mentioned adhesion.

  Moreover, it is preferable that the resin fine particles A have a property of generating an aggregate in an aqueous medium containing the anionic surfactant. In the production method of the present invention, when the resin fine particles A are added to the aqueous medium before emulsification or the emulsified or dispersed liquid after emulsification in the emulsification step, the resin fine particles B do not adhere to the droplets of the toner material. It is not preferable that they exist independently and stably. Since the resin fine particles A have the property of forming aggregates in the aqueous medium containing the anionic surfactant, the resin fine particles A present on the water phase side at the time of emulsification or after the emulsification are used. And can easily adhere to the droplet surface of the toner material. That is, in the aqueous medium containing the anionic surfactant, the resin fine particles A are unstable and normally aggregate, and if there is a toner material droplet, the attractive force with the toner material droplet Is strong, a complex of different particles is formed.

[Preparation Method of Resin Fine Particle A]
As described above, it is preferable that the resin fine particles A have a property of generating aggregates in an aqueous medium containing an anionic surfactant because they easily adhere to the droplet surface of the toner material.
The resin fine particle B having such a property is prepared by adjusting the resin fine particle A in the presence of a nonionic surfactant, an amphoteric surfactant, and a cationic surfactant, or as a resin for the resin fine particle A, an amine group, It can be prepared by using a resin into which a cationic group such as an ammonium base is introduced.

-Cationic surfactant-
Examples of the cationic surfactant include amine salt type surfactants and quaternary ammonium salt type cationic surfactants. Examples of the amine salt type surfactant include alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazolines, and the like. Examples of the quaternary ammonium salt type cationic surfactant include alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride and the like. . Among the cationic surfactants of the quaternary ammonium salt type, aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, perfluoroalkyl (6 to 10 carbon atoms) sulfonamidopropyltrimethylammonium salt, etc. Preferred are aliphatic quaternary ammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts, and the like.
Examples of commercially available cationic surfactants include Surflon S-121 (Asahi Glass Co., Ltd.); Florard FC-135 (Sumitomo 3M Co., Ltd.); Unidyne DS-202 (Daikin Industries Co., Ltd.), MegaFuck F-150, F-824 (Dainippon Ink Co., Ltd.); Xtop EF-132 (To-Chem Products Co., Ltd.);

-Nonionic surfactant-
Examples of the nonionic surfactant include fatty acid amide derivatives and polyhydric alcohol derivatives.

-Amphoteric surfactant-
Examples of the amphoteric surfactant include alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine, N-alkyl-N, N-dimethylammonium betaine, and the like.

In the toner of the present invention, the glass transition temperature (TgA) of the resin fine particles A is higher than the glass transition temperature (Tg core) of the binder resin. At this time, if TgA is not higher than Tg core, the effect of improving the heat resistant storage stability of the toner cannot be obtained.
The difference (TgA-Tgcore) between the glass transition temperature (TgA) of the resin fine particles A and the glass transition temperature (Tgcore) of the binder resin is preferably 30 ° C to 70 ° C, and preferably 45 ° C to 60 ° C. More preferred.
If the TgA-Tg core is less than 30 ° C., the glass transition temperature of the binder resin that exhibits low-temperature fixability cannot be sufficiently lowered, or the glass transition temperature of the resin fine particles B that exhibit heat-resistant storage stability is sufficient. Therefore, it is difficult to achieve both low-temperature fixability and heat-resistant storage stability of the toner. When the TgA-Tg core exceeds 70 ° C., the melt viscosity of the resin fine particles B becomes too high, which may inhibit the low-temperature fixability of the toner.

<Resin fine particle B>
The resin fine particle B is not particularly limited as long as it has a volume average particle diameter of 5 nm to 50 nm, and can be appropriately selected according to the purpose.
Examples of the resin for the resin fine particles B include, for example, vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, and ionomer resin. And polycarbonate resin. These may be used individually by 1 type and may use 2 or more types together.
Among these, a vinyl resin, a polyurethane resin, an epoxy resin, and a polyester resin are preferable, and a vinyl resin is more preferable because an aqueous dispersion of fine spherical resin fine particles can be easily obtained.
The vinyl resin is a polymer obtained by homopolymerization or copolymerization of a vinyl monomer. For example, styrene polymer, acrylate polymer, methacrylic acid ester polymer, styrene- (meth) acrylic acid ester polymer, styrene- Examples include butadiene copolymers, (meth) acrylic acid-acrylic acid ester polymers, styrene-acrylonitrile copolymers, styrene-maleic anhydride copolymers, and styrene- (meth) acrylic acid copolymers.
Among these, a styrene polymer, an acrylic ester polymer, a methacrylic ester polymer, and a combination thereof are preferable.
The resin fine particles B are preferably fine particles of a crosslinked resin containing at least one of a styrene polymer, an acrylic ester polymer, and a methacrylic ester polymer.

The volume average particle diameter of the resin fine particles B is 5 nm to 50 nm, and preferably 10 nm to 25 nm.
The volume average particle size and particle size distribution can be measured by, for example, SEM, TEM, light scattering method, and the like. Among these, it is preferable to measure by a laser scattering measurement method using a laser diffraction / scattering type particle size distribution measuring apparatus (LA-920 manufactured by Horiba Seisakusho), and the sample is diluted to an appropriate concentration so as to enter the measurement range. Just measure.

As a glass transition temperature (TgB) of the said resin fine particle B, 40 to 200 degreeC is preferable and 45 to 80 degreeC is more preferable.
If the TgB is less than 40 ° C., the resin fine particles B on the toner surface may be softened in the toner storage temperature range, and aggregates may be formed due to fusion between the toners. On the other hand, when the TgB exceeds 200 ° C., the toner surface becomes too hard, and the toner may not be sufficiently melted at the time of heat fixing, so that the fixability may be deteriorated.

The weight average molecular weight (Mw) of the resin fine particles B is preferably 10,000 to 800,000, and more preferably 10,000 to 450,000.
When the weight average molecular weight is less than 10,000, it easily swells in an organic solvent or an aqueous medium, so that an aggregate is formed when the toner is fixed on the surface of the toner base particle, and the surface layer of the toner base particle surface is formed. The formation of the layer composed of the resin fine particles B is hindered, and the effect of preventing the resin fine particles A from being buried or moved due to mechanical stress may not be sufficiently obtained. On the other hand, if the weight average molecular weight exceeds 800,000, the toner surface becomes too hard, and the toner may not be sufficiently melted at the time of heat fixing, so that the fixability may be deteriorated.

The resin fine particles B preferably have an anionic property in order not to aggregate the resin fine particles B when the aqueous medium in the toner production method of the present invention contains an anionic surfactant. Thereby, it adsorbs to the outermost shell of the droplet containing the toner material, and has an effect of suppressing coalescence of the droplets, and the particle size distribution of the toner can be controlled. Furthermore, negative chargeability of the toner can be imparted. In order to exert these effects, the resin fine particles B are made smaller than the resin fine particles A, and the volume average particle diameter is set to 5 nm to 50 nm.
The resin fine particle B having an anionic property is prepared by using an anionic surfactant in the method for preparing the resin fine particle B described later, or by introducing an anionic group such as a carboxylic acid group or a sulfonic acid group into the resin. Can do.

-Anionic surfactant-
Examples of the anionic surfactant used for preparing the resin fine particles B include fatty acid salts, alkyl sulfate esters, alkyl aryl sulfonates, alkyl diaryl ether disulfonates, dialkyl sulfosuccinates, alkyl phosphates, and naphthalene sulfones. Acid formalin condensate, polyoxyethylene alkyl phosphate ester salt, glyceryl borate fatty acid ester and the like can be mentioned.

[Preparation method of resin fine particle B]
The resin fine particles B can be obtained by polymerizing precursors such as monomers and oligomers constituting the resin for the resin fine particles B according to a known method appropriately selected according to the purpose. It is preferable to obtain it as a liquid. As a method for preparing the aqueous dispersion of resin fine particles B, for example, the following methods are preferably exemplified.
(1) In the case of vinyl resin, aqueous dispersion of resin fine particles B directly from a vinyl monomer as a starting material by any polymerization reaction selected from suspension polymerization, emulsion polymerization, seed polymerization and dispersion polymerization A method for producing a liquid.
(2) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, and epoxy resin, a precursor (monomer, oligomer, etc.) or a solvent solution thereof was dispersed in an aqueous medium in the presence of an appropriate dispersant. Thereafter, heating or adding a curing agent to cure is performed to produce an aqueous dispersion of resin fine particles B.
(3) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., a precursor (monomer, oligomer, etc.) or a solvent solution thereof (preferably liquid. It may be liquefied by heating). A method in which a suitable emulsifier is dissolved therein and then water is added to perform phase inversion emulsification.
(4) Resin prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) The resin fine particles B are obtained by pulverizing and then classifying, and then dispersed in water in the presence of an appropriate dispersant.
(5) A spray of a resin solution prepared by previously dissolving a resin prepared in a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent. A method of dispersing resin fine particles in water in the presence of a suitable dispersant after obtaining resin fine particles B.
(6) A poor solvent is added to a resin solution in which a resin prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) is dissolved in a solvent. Or by precipitating resin fine particles B by cooling a resin solution previously dissolved in a solvent by heating, and then removing the solvent to obtain resin fine particles. How to disperse into.
(7) A resin solution prepared by previously dissolving a resin prepared by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent is appropriately dispersed. A method of removing the solvent by heating or decompression after being dispersed in an aqueous medium in the presence of an agent (8) Any polymerization reaction such as polymerization reaction (addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization etc. A suitable emulsifier is dissolved in a resin solution prepared by dissolving the resin prepared in the solvent in a solvent, and water is added to perform phase inversion emulsification.

[Resin fine particles C]
The volume average particle size of the resin fine particles C is 40 nm to 150 nm, and preferably 80 nm to 120 nm.
The volume average particle size and particle size distribution can be measured by, for example, SEM, TEM, light scattering method, and the like. Among these, it is preferable to measure by a laser scattering measurement method using a laser diffraction / scattering type particle size distribution measuring apparatus (LA-920 manufactured by Horiba Seisakusho), and the sample is diluted to an appropriate concentration so as to enter the measurement range. Just measure.

As a glass transition temperature (TgC) of the said resin fine particle C, 50 to 200 degreeC is preferable and 55 to 80 degreeC is more preferable.
If the TgC is less than 50 ° C., the resin fine particles C on the toner surface soften in the storage temperature range of the toner, and there is a possibility that an aggregate is formed due to fusion of the toners. On the other hand, if the TgC exceeds 200 ° C., the toner surface becomes too hard, and the toner may not be sufficiently melted at the time of heat fixing, so that the fixability may be deteriorated.

  The weight average molecular weight (Mw) of the resin fine particles C is preferably 10,000 to 800,000, and more preferably 10,000 to 450,000.

  In the toner manufacturing process of the present invention, the resin fine particles C adhere to the outside of the resin fine particles A and B adhering to the surface of the toner base particles.

The resin fine particles C preferably have an anionic property in order not to aggregate the resin fine particles C when the aqueous medium in the toner production method of the present invention contains an anionic surfactant. Thereby, it adsorbs to the outermost shell of the droplet containing the toner material, and has an effect of suppressing coalescence of the droplets, and the particle size distribution of the toner can be controlled. Furthermore, negative chargeability of the toner can be imparted.
The anionic resin fine particles C are prepared by using an anionic surfactant in the method for preparing the resin fine particles C described later, or by introducing an anionic group such as a carboxylic acid group or a sulfonic acid group into the resin. Can do.

-Anionic surfactant-
Examples of the anionic surfactant used for preparing the resin fine particles C include fatty acid salts, alkyl sulfate esters, alkyl aryl sulfonates, alkyl diaryl ether disulfonates, dialkyl sulfosuccinates, alkyl phosphates, and naphthalene sulfones. Acid formalin condensate, polyoxyethylene alkyl phosphate ester salt, glyceryl borate fatty acid ester and the like can be mentioned.

[Preparation Method of Resin Fine Particle C]
The resin fine particles C can be obtained by polymerizing precursors such as monomers and oligomers constituting the resin for the resin fine particles C according to a known method appropriately selected according to the purpose. It is preferable to obtain it as a liquid. As a method for preparing the aqueous dispersion of resin fine particles C, for example, the following methods are preferably exemplified.
(1) In the case of a vinyl resin, aqueous dispersion of resin fine particles C directly by a polymerization reaction selected from a suspension polymerization method, an emulsion polymerization method, a seed polymerization method and a dispersion polymerization method using a vinyl monomer as a starting material A method for producing a liquid.
(2) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, and epoxy resin, a precursor (monomer, oligomer, etc.) or a solvent solution thereof was dispersed in an aqueous medium in the presence of an appropriate dispersant. Then, the method of manufacturing the aqueous dispersion of the resin fine particle C by heating or adding a hardening | curing agent and making it harden | cure.
(3) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., a precursor (monomer, oligomer, etc.) or a solvent solution thereof (preferably liquid. It may be liquefied by heating). A method in which a suitable emulsifier is dissolved therein and then water is added to perform phase inversion emulsification.
(4) Resin prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) The resin fine particles C are obtained by pulverizing and then classifying, and then dispersed in water in the presence of an appropriate dispersant.
(5) A spray of a resin solution prepared by previously dissolving a resin prepared in a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent. A method in which after obtaining resin fine particles C, the resin fine particles are dispersed in water in the presence of an appropriate dispersant.
(6) A poor solvent is added to a resin solution in which a resin prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) is dissolved in a solvent. Or by precipitating resin fine particles C by cooling a resin solution previously dissolved in a solvent by heating, and then removing the solvent to obtain resin fine particles. Then, the resin fine particles C are dissolved in water in the presence of an appropriate dispersant. How to disperse into.
(7) A resin solution prepared by previously dissolving a resin prepared by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent is appropriately dispersed. A method of removing the solvent by heating or decompression after being dispersed in an aqueous medium in the presence of an agent (8) Any polymerization reaction such as polymerization reaction (addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization etc. A suitable emulsifier is dissolved in a resin solution prepared by dissolving the resin prepared in the solvent in a solvent, and water is added to perform phase inversion emulsification.

<Crystalline polyester>
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 for the toner, the heat-resistant storage stability due to crystallinity is good until just before the melting start temperature, and at the melting start temperature, a sharp viscosity drop (sharp melt property) is caused to fix. As a result, 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 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.
In the present invention, the crystalline 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 as described above. It refers to what is done.

-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 a branched type, the crystallinity of the crystalline resin is 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, in terms of high crystallinity of the crystalline resin and excellent sharp melt properties, 1,12-dodecanediol is preferred.
Examples of the trihydric or higher alcohol include glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol. These may be used individually by 1 type and may use 2 or more types together.

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

  Since the crystalline resin has a structural unit derived from a saturated aliphatic dicarboxylic acid and a structural unit derived from a saturated aliphatic diol, the crystallinity is high and the sharp melt property is excellent. It is preferable in that the fixing ability can be exhibited.

The melting point of the crystalline polyester resin is preferably more than 60 ° C. and less than 80 ° C. When the melting point is 60 ° C. or lower, the crystalline resin is easily melted at a constant temperature, and the heat-resistant storage stability of the toner is deteriorated. When the melting point is 80 ° C. or higher, the crystalline resin is not sufficiently melted by heating during fixing. Low temperature fixability deteriorates.
The melting point can be measured by an endothermic peak value of a DSC chart in a differential scanning calorimeter (DSC) measurement.

In addition, the toner of the present invention may contain the following materials. The toner of the present invention can be mixed or polymerized with the binder resin and the colorant to obtain the toner of the present invention. If necessary, a charge control agent, a release agent, a fluidizing agent, and the like can be further contained.
As the colorant, all of dyes and pigments used as toner colorants can be used. Specifically, carbon black, iron black, Sudan black SM, first yellow G, benzidine yellow, solvent yellow (21, 77, 114, etc.), pigment yellow (12, 14, 17, 83, etc.), Indian first orange, Irgasin Red, Paranitaniline Red, Toluidine Red, Solvent Red (17, 49, 128, 5, 13, 22, 48, 2 etc.), Disperse Red, Carmine FB, Pigment Orange R, Lake Red 2G, Rhodamine FB, Rhodamine B lake, methyl violet B lake, phthalocyanine blue, solvent blue (25, 94, 60, 15.3, etc.), pigment blue, brilliant green, phthalocyanine green, oil yellow GG, Kayaset YG, o Tetrazole brown B and oil pink OP, and the like. These may be used alone or in admixture of two or more. Further, if necessary, magnetic powder (a powder of a ferromagnetic metal such as iron, cobalt, nickel, or a compound such as magnetite, hematite, ferrite) can also be included as a colorant. The content of the colorant is preferably 0.1 to 40 parts, more preferably 0.5 to 10 parts, with respect to 100 parts of the toner binder of the present invention. In addition, when using magnetic powder, Preferably it is 20-150 parts, More preferably, it is 40-120 parts. In the above and further below, parts mean parts by weight.

As the mold release agent, those having a softening point of 50 to 170 ° C. are preferable. Polyolefin wax, natural wax (for example, carnauba wax, montan wax, paraffin wax and rice wax), aliphatic alcohol having 30 to 50 carbon atoms ( For example, triacontanol, etc.), fatty acids having 30 to 50 carbon atoms (e.g., triacontane carboxylic acid, etc.), and mixtures thereof. Polyolefin waxes include (co) polymers [obtained by (co) polymerization] of olefins (for example, ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-dodecene, 1-octadecene, and mixtures thereof). And olefin (co) polymer oxides by oxygen and / or ozone, maleic acid modifications of olefin (co) polymers [eg maleic acid and its derivatives (maleic anhydride, Modified products such as monomethyl maleate, monobutyl maleate and dimethyl maleate), olefins and unsaturated carboxylic acids [(meth) acrylic acid, itaconic acid and maleic anhydride, etc.] and / or unsaturated carboxylic acid alkyl esters [(meta ) Alkyl acrylate (alkyl of 1 to 18 carbon atoms) ester and Copolymers with alkyl oleate (alkyl 1 to 18 carbon esters) and the like, polymethylene (eg Fischer-Tropsch wax such as sazol wax), fatty acid metal salts (eg calcium stearate), fatty acid ester (behenine) Acid behenyl and the like).
As charge control agents, nigrosine dyes, triphenylmethane dyes containing tertiary amines as side chains, quaternary ammonium salts, polyamine resins, imidazole derivatives, quaternary ammonium base-containing polymers, metal-containing azo dyes, copper phthalocyanine dyes , Salicylic acid metal salts, boron complexes of benzylic acid, sulfonic acid group-containing polymers, fluorine-containing polymers, halogen-substituted aromatic ring-containing polymers, metal complexes of salicylic acid alkyl derivatives, cetyltrimethylammonium bromide, and the like.

  As a fluidizing agent, colloidal silica, alumina powder, titanium oxide powder, calcium carbonate powder, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, silica sand, clay, mica, wollastonite, Examples thereof include diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, and barium carbonate.

The composition ratio when the toner is formed is based on the toner weight (% in the following paragraph is weight%), and the toner binder of the present invention is preferably 30 to 97%, more preferably 40 to 95%, particularly Preferably 45 to 92%; Colorant is preferably 0.05 to 60%, more preferably 0.1 to 55%, and particularly preferably 0.5 to 50%; Preferably 0 to 30%, more preferably 0.5 to 20%, particularly preferably 1 to 10%; the charge control agent is preferably 0 to 20%, more preferably 0.1 to 10%, particularly preferably 0.5 to 7.5%; The fluidizing agent is preferably 0 to 10%, more preferably 0 to 5%, and particularly preferably 0.1 to 4%. The total content of additives is preferably 3 to 70%, more preferably 4 to 58%, and particularly preferably 5 to 50%.
When the composition ratio of the toner is in the above range, a toner having good chargeability can be easily obtained.

As described above, the toner of the present invention may be obtained by any conventionally known method such as a kneading and pulverizing method, an emulsion phase inversion method, or a polymerization method. For example, when a toner is obtained by a kneading and pulverizing method, the components constituting the toner excluding the fluidizing agent are dry blended, and then melt-kneaded, then coarsely pulverized, and finally atomized using a jet mill pulverizer or the like. Further, by further classifying, the volume average particle diameter (D50) is preferably made into fine particles having 5 to 20 μm, and then mixed with a fluidizing agent. The particle size (D50) is measured using a Coulter counter [for example, trade name: Multisizer III (manufactured by Coulter)].
When the toner is obtained by the emulsion phase inversion method, the components constituting the toner excluding the fluidizing agent can be dissolved or dispersed in an organic solvent, and then emulsified by adding water, etc., and then separated and classified for production. Moreover, you may manufacture by the method of using the organic microparticles of Unexamined-Japanese-Patent No. 2002-284881. The volume average particle diameter of the toner is preferably 3 to 15 μm.
If necessary, the toner is mixed with carrier particles (iron powder, glass beads, nickel powder, ferrite, magnetite, and ferrite whose surface is coated with resin (acrylic resin, silicone resin, etc.)), and an electric latent image is obtained. It can be used as a developer. Further, instead of the carrier particles, an electric latent image can be formed by friction with a charging blade or the like.
The electric latent image is fixed on a support (paper, polyester film, etc.) by a known hot roll fixing method or the like.

[Method for Producing Toner of the Present Invention]
The method for producing the toner of the present invention is not particularly limited. For example, a solution or dispersion of an organic solvent obtained by dissolving or dispersing a toner material containing at least a binder resin is emulsified or dispersed in an aqueous medium. It can be prepared by removing the organic solvent from the emulsified or dispersed liquid. Preferably, a solution or dispersion formed by dissolving or dispersing a toner material mainly composed of amorphous polyester or an amorphous polyester precursor and a colorant in an organic solvent is used as styrene / acrylic resin fine particles and Emulsified or dispersed in an aqueous medium containing acrylic resin fine particles to prepare an emulsified or dispersed liquid, granulated, and after adhering acrylic resin fine particles to the toner precursor containing the emulsified or dispersed toner material, the organic solvent was removed. Then, after the toner particles are formed, water containing the toner particles is heat-treated to produce a desired toner. More preferably, a solution or dispersion of a toner material containing an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound is emulsified or dispersed in an aqueous medium, and active hydrogen is contained in the aqueous medium. A desired toner is produced by producing toner precursor particles including an adhesive substrate obtained by reacting a group-containing compound and a polymer capable of reacting with an active hydrogen group-containing compound, and attaching acrylic resin fine particles. .

(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 polyester, 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.

(Removal of organic solvent)
The organic solvent is removed from the emulsified slurry obtained by emulsification or dispersion. The organic solvent is removed by (1) a method of gradually raising the temperature of the entire reaction system to completely evaporate and remove the organic solvent in the oil droplets, and (2) spraying the emulsified dispersion in a dry atmosphere, Examples thereof include a method in which the water-insoluble organic solvent in the droplets is completely removed to form toner fine particles, and the aqueous dispersant is removed by evaporation. When the organic solvent is removed, toner particles are formed.

(Washing)
After removing the organic solvent to form toner particles, the formed toner particles are washed with ion-exchanged water to prepare a dispersion having a desired conductivity.

(Heat treatment)
The dispersion is heated. Examples of the heat treatment include (1) a method of heat-treating in a stationary state, and (2) a method of heat-treating with stirring, and when heat-treated, toner particles having a smooth surface are formed. Further, when the toner particles are dispersed with ion-exchanged water, the heat treatment may be performed before or after cleaning.

(Dry)
The formed toner particles are dried and then classified as desired.
The classification is performed, for example, by removing fine particle portions in a liquid by a cyclone, a decanter, centrifugation, or the like. The classification operation may be performed after obtaining the powder after drying.

  The toner particles thus obtained are mixed with particles such as a colorant, a release agent, and a charge control agent, and further a mechanical impact force is applied to the particles such as a release agent from the surface of the toner particles. Can be prevented from desorbing. As a method of applying a mechanical impact force, for example, a method of applying an impact force to a mixture with a blade rotating at high speed, a mixture of particles in a high-speed air stream and acceleration to mix particles or a composite particle is a suitable collision plate. And the like. As an apparatus used in this method, for example, an ong mill (manufactured by Hosokawa Micron Co., Ltd.), an I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) and a pulverization air pressure is lowered, and a hybridization system (Nara Machinery). Mfg. Co., Ltd.), Kryptron System (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar, and the like.

  Hereinafter, the present invention will be described in more detail and specifically based on examples and comparative examples, but these examples are for facilitating understanding of the essence of the present invention. It is not meant to be limiting. In the following description, “parts” and “%” represent “parts by weight” and “% by weight” unless otherwise specified.

<Preparation of resin fine particles A>
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 A1] was obtained.
[Styrene / acrylic resin fine particle dispersion A1] has a volume average particle size (measured by LA-920 manufactured by Horiba, Ltd.) of 14 nm, an acid value of 45 mg KOH / g, a molecular weight Mw of 300,000, Tg of 60 ° C., and T1 / 2. Was 170 ° C.

<Preparation of resin fine particle B>
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 B1]. [Acrylic resin fine particle B1] has 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, Tg of 82 ° C., and T1 / 2 of 139 ° C. there were.

<Adjustment of resin fine particles C>
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), 160 parts of methyl methacrylate, 34 parts of butyl acrylate, 1 part of ammonium persulfate, ethylene glycol When 1 part of dimethacrylate was charged and stirred for 15 minutes at 400 rpm, a white emulsion was obtained. The mixture was heated to raise the temperature in the system to 65 ° C. and reacted for 10 hours. Furthermore, 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 C1]. [Acrylic resin fine particles C1] has a volume average particle size (measured with LA-920 manufactured by Horiba, Ltd.) of 72 nm, an acid value of 2 mgKOH / g, a molecular weight Mw of 32,000, Tg of 81 ° C., and T1 / 2 of 135 ° C. there were.

<Synthesis of Amorphous Polyester D>
(Synthesis of amorphous polyester D1)
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 200 ° C. For 5 hours to obtain a prepolymer C1.
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 an amorphous polyester resin D1. The molecular weight Mw of the amorphous polyester D1 was 150,000, and Tg was −40 ° C.

(Synthesis of amorphous polyester D2)
In the same manner, amorphous polyester D2 was synthesized in which 3-methyl-1,5-pentanediol was 100 mol% and the dicarboxylic acid component was 100 mol% isophthalic acid. The molecular weight Mw of D2 was 110000, and Tg was 5 ° C.

(Synthesis of amorphous polyester D3)
Further, in the same manner, an amorphous polyester D3 was synthesized in which 3-methyl-1,5-pentanediol was 100 mol% and the dicarboxylic acid component was 100 mol% decanedioic acid.
The molecular weight Mw of D3 was 100,000, and Tg was −65 ° C.

<Synthesis of amorphous polyester E>
(Synthesis of amorphous polyester E1)
A four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, bisphenol A ethylene oxide side 2 mol adduct / bisphenol A propylene oxide 3 mol adduct in a molar ratio of 85/15, isophthalic acid And adipic acid at a molar ratio of 80/20, OH / COOH, which is the molar ratio of hydroxyl group to carboxyl group, was charged at 1.3, and reacted with 500 ppm of titanium tetraisopropoxide at 230 ° C. at normal pressure for 8 hours. Furthermore, after reacting at a reduced pressure of 10 mmHg to 15 mmHg for 4 hours, trimellitic anhydride was added to the reaction vessel so as to be 1 mol% based on the total resin components, and reacted at 180 ° C. and normal pressure for 3 hours to obtain amorphous polyester resin E1 Got. The molecular weight Mw of the amorphous polyester E1 was 5000, and the Tg was 48 ° C.

(Synthesis of amorphous polyester E2)
In the same manner, the molar ratio of bisphenol A ethylene oxide side 2 adduct is 100, the molar ratio of isophthalic acid and adipic acid is 95/5, and the molar ratio of hydroxyl group to carboxyl group is 1.15. Amorphous polyester E2 was synthesized. The molecular weight Mw of E2 was 8000, and Tg was 72 ° C.

(Synthesis of amorphous polyester E3)
In the same manner, the molar ratio of bisphenol A ethylene oxide side 2 mol adduct / bisphenol A propylene oxide 3 mol adduct was 75/25, isophthalic acid and adipic acid 65/35, hydroxyl group and carboxyl group. Amorphous polyester E3 having a molar ratio of OH / COOH of 1.4 was synthesized. E3 had a molecular weight Mw of 4000 and Tg of 38 ° C.

<Synthesis of crystalline polyester resin>
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 the pressure of 8.3 kPa for 2 hours, and crystalline polyester resin was obtained. The molecular weight Mw was 15000 and Tg was 70 ° C.

<Master batch (MB) adjustment>
1000 parts by mass of water, 540 parts by mass of carbon black (“Printex35”; manufactured by Degussa, DBP oil absorption = 42 ml / 100 g, pH = 9.5), and 1100 parts by mass of the unmodified polyester were combined with a Henschel mixer (Mitsui Mine). Mixed). The mixture was kneaded for 30 minutes at 150 ° C. with two rolls, rolled and cooled, and pulverized with a pulverizer (manufactured by Hosokawa Micron) to prepare a master batch.

<Preparation of WAX dispersion>
A container equipped with a stir bar and a thermometer was charged with 50 parts of ester wax and 450 parts of ethyl acetate as a release agent. The temperature was raised to 80 ° C. with stirring and held at 80 ° C. for 5 hours. 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 Then, dispersion was performed to obtain [WAX dispersion].

<Creation of crystalline polyester dispersion>
A container equipped with a stirrer and a thermometer was charged with 50 parts of crystalline polyester and 450 parts of ethyl acetate, heated to 80 ° C. with stirring, held at 80 ° C. for 5 hours, and then 30 ° C. for 1 hour. Then, using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), the liquid feeding speed is 1 kg / hr, the disk peripheral speed is 6 m / sec, 0.5% zirconia beads are filled at 80% by volume, and dispersed under the conditions of 3 passes. To obtain a [crystalline polyester dispersion].

<Manufacture of toner>
A specific preparation example of the toner used for the evaluation will be described. The toner used in the present invention is not limited to these examples.

[Example 1: Production of toner a]
-Adjustment of toner material phase-
[WAX dispersion] 500 parts, [Amorphous polyester D1] 300 parts, [Crystalline polyester resin dispersion] 500 parts, [Amorphous polyester D2] 700 parts, [Masterbatch 1] 100 parts and [Ketimine compound] 1] Two parts were put into a container and mixed at 5,000 rpm for 60 minutes with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) to obtain a toner material dissolved or dispersed liquid.

-Preparation of aqueous medium phase-
990 parts of water, 83 parts by weight of the styrene / acrylic resin fine particle dispersion A1, 37 parts by weight of an aqueous solution of 48.5% by weight of sodium dodecyl diphenyl ether disulfonate (“Eleminol MON-7”; manufactured by Sanyo Chemical Industries), and ethyl acetate 90 parts by mass were mixed and stirred to obtain a milky white liquid (aqueous phase). Further, 166 parts by weight of acrylic resin fine particles B1 were added. When observed with an optical microscope, several hundred μm aggregates were observed. When this aqueous medium phase was stirred at 8000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), it was confirmed by an optical microscope that the aggregates were loosened and could be dispersed into small aggregates of several μm. Therefore, it was expected that the acrylic resin fine particles B1 were dispersed and adhered to the droplets of the toner material component in the subsequent emulsification step of the toner material. As described above, the acrylic resin fine particles B1 cause aggregation but are loosened by shearing, which is important for uniform adhesion to the toner surface.

~ Emulsification or preparation of dispersion ~
150 parts by mass of the aqueous medium phase is put in a container, and stirred using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) at a rotational speed of 11000 rpm. To this, 100 parts by mass of the toner material dissolved or dispersed is added. The mixture was mixed for 10 minutes to prepare an emulsification or dispersion (emulsion slurry).

~ Removal of organic solvent ~
Into a flask equipped with a deaeration pipe, a stirrer and a thermometer, 100 parts by mass of the emulsified slurry was charged, and the solvent was removed under reduced pressure at 30 ° C. for 12 hours while stirring at a stirring peripheral speed of 20 m / min. did.

~Washing~
After filtering the whole amount of the solvent-removed slurry under reduced pressure, 300 parts by mass of ion-exchanged water was added to the filter cake, mixed with a TK homomixer, redispersed (at a rotation speed of 11000 rpm for 10 minutes) and then filtered. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed with a TK homomixer (at a rotation speed of 11000 rpm for 10 minutes) and then filtered three times. The conductivity of the redispersed slurry was 0. When it became 1 μS / cm or more and 10 μS / cm or less, a cleaning slurry was obtained.

~ Heat treatment ~
After fixing the fine particles B1 adhering to the toner surface by heating in a flask equipped with a stirrer and a thermometer while stirring the resulting cleaning slurry at 50 ° C. for 60 minutes while stirring at a peripheral speed of 20 m / min. Filtered.

~ Dry ~
The obtained filter cake was dried at 45 ° C. for 48 hours with a forward air dryer and sieved with a mesh having a mesh size of 75 μm to obtain toner base particles a.

~ External treatment ~
To 100 parts by mass of toner base particles a, 0.6 parts by mass of hydrophobic silica having an average particle size of 100 nm, 1.0 part by mass of titanium oxide having an average particle size of 20 nm, and hydrophobic silica fine powder having an average particle size of 15 nm 0.8 part of the body was mixed with a Henschel mixer to obtain toner a.

[Example 2: Production of toner b]
A toner b was obtained in the same manner except that the amorphous polyester D1 of Example 1 was changed to D2.

[Example 3: Production of toner c]
A toner c was obtained in the same manner except that the amorphous polyester D1 of Example 1 was changed to D3.

[Example 4: Production of toner d]
A toner d was obtained in the same manner except that the amorphous polyester E1 of Example 1 was changed to E2.

[Example 5: Production of toner e]
A toner e was obtained in the same manner except that the amorphous polyester E1 of Example 1 was changed to E3.

[Example 6: Production of toner f]
A toner f was obtained in the same manner as in Example 1 except that the crystalline polyester was omitted.

[Comparative Example 1: Production of Toner g]
A toner g was obtained in the same manner as in Example 1 except that the resin fine particles A1 were removed.

[Comparative Example 2: Production of Toner h]
A toner h was produced in the same manner except that the resin fine particles B1 were removed from Example 1, but the particles were unstable and could not be granulated.

[Comparative Example 3: Production of Toner i]
A toner i was obtained in the same manner as in Example 1 except that the resin fine particles C1 were omitted.

[Comparative Example 5: Production of toner j]
Although a prototype was made in the same manner except that the resin fine particles A1, B1, and C1 were removed from Example 1, it was difficult to produce the particles.

(Fixing lower limit temperature)
The fixing unit of the Ricoh full-color MFP Imagio NeoC600Pro has been modified so that the temperature and linear velocity can be adjusted, and transfer paper for plain paper and cardboard (type 6000 <70W> made by Ricoh Co., Ltd. and copy printing) Fixation was evaluated with a solid image on paper <135>) with a toner adhesion amount of 0.85 ± 0.1 mg / cm ² . The fixing roll temperature at which the residual ratio of the image density after rubbing the fixed image with a pad becomes 70% or more was determined as the minimum fixing temperature.
Evaluation criteria are
A: Less than 120 ° C. O: Less than 140 ° C. 120 ° C. or more Δ: Less than 160 ° C. 140 ° C. or more X: 160 ° C. or more

(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

(Charging environment stability)
Using a Ricoh digital full-color copier, imgioColor2800, while a 100,000 color image chart with 7% image area was output in a single color mode, a part of the developer was sampled every 1000 sheets and the charge amount was measured by the blow-off method. Was measured to evaluate the charging stability. The high-temperature and high-humidity environment charging stability evaluation was performed in an environment of a temperature of 40 ° C. and a humidity of 90%, and the low-temperature low-humidity environment charging stability evaluation was performed in an environment of a temperature of 10 ° C. and a humidity of 15%.
Evaluation criteria are
A: Change in charge amount is less than 3 μc / g ○: Change in charge amount is 3 μc / g or more and less than 5 μc / g Δ: Change in charge amount is 5 μc / g or more and less than 10 μc / g ×: Change in charge amount is 10 μc / g g or more.
Tables 1 and 2 show the evaluation results of the toners obtained in Examples 1 to 6 and Comparative Examples 1 to 4, respectively.

As described above, in Examples 1 to 6, toners having excellent low-temperature fixability, heat-resistant storage stability, and charging environment stability were obtained.
In Comparative Example 1, since the resin fine particles A are not blended, it is considered that the resin fine particles B and C alone are not enough to form a film with the shell, and the heat resistant storage stability is deteriorated.
In Comparative Example 3, since the outermost resin fine particles C were not present, the heat resistant storage stability was deteriorated, and the charging stability was also deteriorated. From this, it is considered that the resin fine particles C also affect the charging stability.
In Comparative Examples 2 and 4, since there are no resin fine particles stabilizing particles on the toner surface, granulation cannot be performed.

Japanese Patent Laid-Open No. 11-133665 JP 2002-287400 A JP 2002-351143 A Japanese Patent No. 2579150 JP 2001-158819 A JP 2004-46095 A JP 2007-271789 A

Claims (11)

  Toner particles having at least a binder resin, a colorant, and a release agent and having a core / shell structure, wherein the shell is composed of a layer A composed of styrene / acrylic resin particles, a layer B composed of acrylic resin particles, And the shell layer A is provided outside the shell layer B, and the shell layer C is provided on the outermost surface.   2. The toner according to claim 1, wherein the glass transition temperature at the first temperature increase is higher than 20 ° C. and lower than 40 ° C. 3.   The toner according to claim 1, wherein Tg1st−Tg2nd is 10 ° C. or more.   The toner according to claim 1, further comprising a crystalline resin in the core.   The resin fine particles for the resin fine particle layer A are fine particles of a crosslinked resin containing at least one of a styrene polymer, an acrylate polymer, and a methacrylic ester polymer, and a glass transition temperature is 40 ° C. The toner according to claim 1, wherein the toner is more than 200 ° C.   The resin fine particle layer B is fine particles of a crosslinked resin containing at least one of an acrylate polymer and a methacrylic ester polymer, and has a glass transition temperature of more than 50 ° C and less than 110 ° C. The toner according to claim 5.   7. The toner according to claim 1, wherein the resin fine particle layer C is fine particles of a crosslinked resin containing at least one of an acrylate polymer and a methacrylate polymer. .   The binder resin comprises two kinds of amorphous polyester, and one resin D of the amorphous polyester is a polyester having a glass transition temperature of -60 ° C. or higher and lower than 0 ° C. and having a branched structure. 2. A polyester modified with a functional group capable of bonding with urea or urethane, wherein the other resin E of the amorphous polyester is an unmodified polyester having a glass transition temperature of more than 40 ° C. and less than 70 ° C. The toner according to claim 7.   The toner according to claim 1, wherein the toner is produced by granulation in an aqueous medium.   An electrostatic latent image developer comprising the toner according to claim 1 and a carrier.   An electrostatic latent image carrier, charging means for charging the surface of the electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and 9. A developing unit for developing the latent image with the toner according to claim 8, a transfer unit for transferring the toner image to the image carrying medium, and a toner image on the image carrying medium. An image forming apparatus comprising fixing means for fixing the toner.