JP2015187715A - Manufacturing method of toner and toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of a toner that can achieve a heat-resistant storage property, humidity and heat-resistant storage property, and low-temperature fixability, and is excellent in toner durability and glossiness.SOLUTION: There is provided a manufacturing method of a toner (Z) containing a colorant, a crystalline resin (A), and a vinyl resin (B) having an ester group, the manufacturing method including a step of heating to fuse first an aggregate (Y) formed by aggregating dispersion elements (X) in a fluid dispersion (W) containing the crystalline resin (A) and the vinyl resin (B) to obtain resin particles (Z').

Description

  The present invention relates to a method for producing a toner used for developing a latent image formed in an electrophotographic method, an electrostatic recording method, an electrostatic printing method or the like.

Currently, from the viewpoint of energy saving, electrophotographic toners are desired to have both heat-resistant storage stability, moisture-heat storage resistance and low-temperature fixability. In order to solve this problem, there has been proposed a method for achieving both a reduction in fixing temperature and heat-resistant storage stability by incorporating a crystalline polyester into an amorphous polyester (Patent Document 1). However, although this method gives good results with respect to low-temperature fixability and heat-resistant storage stability, the crystalline polyester is compatible with the amorphous polyester in the toner production process, and the wet heat-resistant storage stability and durability of the toner are reduced. There was a problem that the design of copiers and printers was limited.
In order to solve these problems, a technique for incorporating a crystalline polyester resin into a styrene-acrylic resin has been proposed (Patent Document 2). By using a styrene-acrylic resin, the durability is improved by controlling the structure so as to have a clear boundary without being compatible with the crystalline resin. However, since crystalline polyester and styrene-acrylic resin have poor compatibility, sufficient low-temperature fixability cannot be obtained, and gloss of printed images is insufficient.

JP 2006-091882 A JP2013-080112A

An object of the present invention is to provide a method for producing a toner that can achieve both heat-resistant storage stability, moisture-heat storage resistance and low-temperature fixability, and is excellent in toner durability and gloss.

The inventor of the present invention has arrived at the present invention as a result of diligent studies to develop a method for producing a toner having both heat-resistant storage stability, moisture-heat storage resistance and low-temperature fixability.
That is, the present invention is a method for producing a toner (Z) containing a colorant, a crystalline resin (A), and a vinyl resin (B) having an ester group, and firstly, the colorant and the crystalline resin (A). And a step of heating and fusing the aggregate (Y) obtained by aggregating the dispersion (X) in the dispersion (W) containing the vinyl resin (B) to obtain resin particles (Z ′). Is a method for producing toner (Z).

  The toner production method of the present invention can produce a toner having both heat resistance storage stability, moisture heat storage resistance and low-temperature fixability, and excellent toner durability and gloss.

The toner (Z) of the present invention is characterized by containing a colorant, a crystalline resin (A), and a vinyl resin (B) having an ester group.
The manufacturing method includes, for example, the following three steps.
(1) A dispersion (W) containing a colorant, a crystalline resin (A), and a vinyl resin (B) is obtained.
(2) Aggregate (Y) obtained by aggregating dispersion (X) in dispersion (W) is obtained.
(3) The aggregate (Y) is heated and fused to obtain resin particles (Z ′).

The crystalline resin in the present invention means a resin having an endothermic peak temperature of melting heat (hereinafter abbreviated as Ta) having an endothermic peak in differential scanning calorimetry (DSC). Ta can be measured by the following method.

<Ta measurement method>
Using a differential scanning calorimeter {for example, “DSC210” [manufactured by Seiko Instruments Inc.]}, the measurement is performed according to the following procedure.
(1) As pretreatment, the sample was heated to 150 ° C. and melted using DSC, then cooled from 150 ° C. to 70 ° C. at a rate of 1.0 ° C./min, and then from 70 ° C. to 10 ° C. Is cooled at a rate of 0.5 ° C./min.
(2) The sample is heated for the second time to 150 ° C. by DSC at a temperature rising rate of 20 ° C./min, and the endothermic change is measured. A graph of “endothermic heat generation” and “temperature” is drawn, and the endothermic peak temperature observed at the second temperature increase is Ta ′. When there are a plurality of peaks, the peak temperature having the largest endothermic amount is defined as Ta ′.
(3) Since Ta ′ was found in (2), a new sample was heated to 150 ° C. and melted using a thermostatic bath, and then cooled from 150 ° C. to (Ta′-15) ° C. And then stored at (Ta′-10) ° C. for 6 hours. By this operation, the sample is annealed.
(4) The annealed sample is cooled to 0 ° C. by DSC at a temperature drop rate of 10 ° C./min.
(5) The temperature is increased again at a rate of temperature increase of 20 ° C./minute, the endothermic change is measured, a similar graph is drawn, and the maximum temperature of the endothermic peak is Ta.

The crystalline resin (A) in the present invention includes a crystalline polyester resin (A1), a crystalline polyurethane resin (A2), a crystalline polyurea resin (A3), a crystalline polyamide resin (A4), and a crystalline vinyl resin (A5). ), Crystalline epoxy resin (A6), crystalline polyether resin (A7), and the like.
(A) may be used alone or in combination of two or more.

As crystalline polyester resin (A1), what has diol (1) and dicarboxylic acid (2) as a structural unit is mentioned. However, monofunctional and trifunctional or higher functional alcohol components and acid components may be used in combination as necessary.

Examples of the diol (1) include alkylene glycols having 2 to 30 carbon atoms (for example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, octanediol). Nonanediol, decanediol, dodecanediol, tetradecanediol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, etc.);
Number average molecular weight (hereinafter abbreviated as Mn) = 106 to 10,000 alkylene ether glycol (for example, diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.) An alicyclic diol having 6 to 24 carbon atoms (for example, 1,4-cyclohexanedimethanol and hydrogenated bisphenol A);
Alkylene oxide of the alicyclic diol having Mn = 100 to 10,000 (hereinafter, “alkylene oxide” may be abbreviated as AO) adduct (addition mole number 2 to 100) [for example, 1,4-cyclohexane Dimethanol ethylene oxide (hereinafter, "ethylene oxide" may be abbreviated as EO) 10 mol adduct, etc.]
AO [EO, propylene oxide (hereinafter, “propylene oxide”) of bisphenols having 15 to 30 carbon atoms (such as bisphenol A, bisphenol F, and bisphenol S) or polyphenols having 12 to 24 carbon atoms (such as catechol, hydroquinone, and resorcin). May be abbreviated as PO) and butylene oxide, etc.] adducts (additional mole number 2-100) (for example, bisphenol A · EO 2-4 mol adduct and bisphenol A · PO 2-4 mol adduct, etc.); weight Average molecular weight (hereinafter sometimes abbreviated as Mw) = 100-5,000 polylactone diol (for example, poly-ε-caprolactone diol, etc.);
Examples thereof include polybutadiene diol having Mw = 1,000 to 20,000.

Among these, alkylene glycols having 2 to 30 carbon atoms and polylactone diols having Mw = 100 to 5,000 are preferable, and ethylene glycol, 1,3-propylene glycol, and 1,4-butane are more preferable. Diol, 1,6-hexanediol, octanediol, nonanediol, decanediol, and dodecanediol.

Examples of the monovalent alcohol component used in combination as necessary include aliphatic monoalcohols and aromatic monoalcohols. When monoalcohol is also used, one type may be used, or two or more types may be used in combination.
Examples of the aliphatic monoalcohol include chain saturated monoalcohol and chain unsaturated monoalcohol.
Examples of the chain saturated monoalcohol include linear or branched chain saturated monoalcohol having 1 to 30 carbon atoms (methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, butanol, pentanol, 2-methyl-1-butanol, 2,2-dimethyl-1-propanol, hexanol, 4-methyl-1-pentanol, 2,3-dimethyl-2-butanol, heptanol, 3-ethyl-3-pentanol, octanol, 2-ethyl-1- Hexanol, nonanol, 2,6-dimethyl-4-heptanol, decanol, undecanol, lauryl alcohol, myristyl alcohol, cetyl alcohol and stearyl alcohol), and linear or branched chain saturated monoalcohol having 1 to 30 carbon atoms. AO with 2 to 4 carbon atoms (EO, PO Fine BO) obtained by adding the (addition molar number of 1 to 20 mol), and the like.

Examples of the chain unsaturated monoalcohol include linear or branched chain unsaturated monoalcohol having 2 to 30 carbon atoms (allyl alcohol, 2-buten-1-ol, 2-penten-1-ol, 2-hexene- 1-ol, 2-hepten-1-ol, 2-octen-1-ol, 2-nonen-1-ol, 2-decen-1-ol, 2-dodecenol, palmitolyl alcohol, oleyl alcohol and linoleyl alcohol Etc.), and those obtained by adding AO (EO, PO, and BO) having 2 to 4 carbon atoms to linear or branched chain-type unsaturated monoalcohol having 1 to 30 carbon atoms (addition mole number 1 to 20 moles), etc. Is mentioned.

As the aromatic monoalcohol, an aromatic monoalcohol having 6 to 30 carbon atoms (phenol, ethylphenol, isobutylphenol, pentylphenol, octylphenol, dodecylphenol, tetradecylphenol, benzyl alcohol, etc.); and 6 to 30 carbon atoms Examples include aromatic monoalcohols added with AO (EO, PO, and BO) having 2 to 4 carbon atoms (added mole number of 1 to 20 moles).
Of these, aliphatic monoalcohols are preferred, and chain saturated monoalcohols are more preferred.

The trihydric or higher alcohol component used in combination as necessary includes 3 to 8 or higher polyhydric aliphatic alcohols having 3 to 36 carbon atoms (alkane polyols and intramolecular or intermolecular dehydrates such as glycerin, Methylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, and polyglycerol; sugars and derivatives thereof such as sucrose and methylglucoside; and AO adducts of trisphenols (such as trisphenol PA) (addition mole number 2) 30); AO adducts (no. Of added moles of 2 to 30) of novolak resins (phenol novolak, cresol novolak, etc.);
Acrylic polyol [hydroxyethyl (meth) acrylate and other vinyl monomer copolymer, etc.]; and the like.
Of these, preferred are polyhydric aliphatic alcohols having 3 to 8 or more valences.

Examples of the dicarboxylic acid (2) include alkane dicarboxylic acids having 4 to 32 carbon atoms (for example, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, and octadecanedicarboxylic acid); alkene dicarboxylic acids having 4 to 32 carbon atoms. (Eg, maleic acid, fumaric acid, citraconic acid, mesaconic acid, etc.); branched alkene dicarboxylic acids having 8 to 40 carbon atoms [eg, dimer acid, alkenyl succinic acid (dodecenyl succinic acid, pentadecenyl succinic acid, and octadecenyl succinic acid) Branched alkane dicarboxylic acids having 12 to 40 carbon atoms [eg alkyl succinic acid (decyl succinic acid, dodecyl succinic acid and octadecyl succinic acid etc.); aromatic dicarboxylic acids having 8 to 20 carbon atoms (eg phthalic acid, isophthalic acid, etc.) , Terephthalic acid and naphthalenedicarboxylic acid, etc.) And the like.
Of these, preferred are alkane dicarboxylic acids having 4 to 32 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms, and more preferred are succinic acid, adipic acid, sebacic acid, azelaic acid, and dodecanedicarboxylic acid. , Octadecanedicarboxylic acid, isophthalic acid, and terephthalic acid.

Examples of the monovalent acid component used in combination include aliphatic monocarboxylic acids and aromatic monocarboxylic acids. In addition, monocarboxylic acid may be used independently and may use 2 or more types together.
Examples of the aliphatic monocarboxylic acid include a chain saturated monocarboxylic acid, a chain unsaturated monocarboxylic acid, and an alicyclic monocarboxylic acid.

As the chain saturated monocarboxylic acid, a linear or branched chain saturated monocarboxylic acid having 2 to 30 carbon atoms (acetic acid, propionic acid, butyric acid, valeric acid, 2-ethylhexanoic acid, caproic acid, enanthic acid, capryl) Acid, pelargonic acid, capric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, tuberculostearic acid, arachidic acid, behenic acid and lignoceric acid).

As the chain unsaturated monocarboxylic acid, a linear or branched chain unsaturated monocarboxylic acid having 3 to 30 carbon atoms (acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, palmitoleic acid, oleic acid, vaccenic acid , Linoleic acid, α-linolenic acid, γ-linolenic acid, eleostearic acid, 8,11-eicosadienoic acid, 5,8,11-eicosatrienoic acid, arachidonic acid, stearidonic acid, eicosapentaenoic acid, docosapentaene Acid, docosahexaenoic acid, dihomo-γ-linolenic acid, elaidic acid, erucic acid, and nervonic acid).

Examples of the alicyclic monocarboxylic acid include alicyclic monocarboxylic acids having 4 to 14 carbon atoms (such as cyclopropane carboxylic acid, cyclobutane carboxylic acid, cyclopentane carboxylic acid, cyclohexane carboxylic acid, and cycloheptane carboxylic acid). .

Examples of the aromatic monocarboxylic acid include aromatic monocarboxylic acids having 7 to 36 carbon atoms, specifically, benzoic acid, vinyl benzoic acid, toluic acid, dimethyl benzoic acid, t-butyl benzoic acid, and cumic acid. , Naphthoic acid, biphenyl monocarboxylic acid and furic acid.
Of these, aliphatic monocarboxylic acids are preferred, and chain saturated monocarboxylic acids are more preferred.

Examples of the trivalent or higher acid component used in combination include aromatic carboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, etc.), and aliphatics having 6 to 36 carbon atoms (including alicyclic). ) Carboxylic acid (hexanetricarboxylic acid, decanetricarboxylic acid, etc.), and ester-forming derivatives and acid anhydrides thereof.
Of these, trimellitic acid, pyromellitic acid, and acid anhydrides thereof are preferable.

From the viewpoint of heat-resistant storage stability, the crystalline polyester resin (A1) preferably has a total carbon number of 8 or more, more preferably 10 or more, particularly as a constituent unit of the diol (1) and the dicarboxylic acid (2). The total carbon number is preferably 52 or less, more preferably 45 or less, particularly preferably 45 or less, most preferably 40 or less, most preferably 12 or more, and most preferably 14 or more, from the viewpoint of low-temperature fixability of the toner (Z). Preferably it is 30 or less.

As the crystalline polyurethane resin (A2), the diol (1) and / or the diamine (3) and the diisocyanate (4) as structural units (A21), the crystalline polyester resin (A1), the diol (1 And / or diamine (3) and diisocyanate (4) as structural units (A22), crystalline polyester resin (A1) and diisocyanate (4) as structural units (A23), and the like.
You may use a monofunctional and trifunctional or more than trifunctional alcohol component, an acid component, and an isocyanate component as needed.

Examples of the diamine (3) include aliphatic diamines having 2 to 18 carbon atoms and aromatic diamines having 6 to 20 carbon atoms.
Examples of the aliphatic diamine having 2 to 18 carbon atoms include a chain aliphatic diamine and a cyclic aliphatic diamine.

  Examples of chain aliphatic diamines include alkylene diamines having 2 to 12 carbon atoms (ethylene diamine, propylene diamine, trimethylene diamine, tetramethylene diamine, hexamethylene diamine, etc.) and polyalkylene (2 to 6 carbon atoms) polyamines [diethylene triamine, imino. Bispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.].

  Cycloaliphatic polyamines include alicyclic diamines having 4 to 15 carbon atoms {1,3-diaminocyclohexane, isophorone diamine, mensen diamine, 4,4'-methylene dicyclohexane diamine (hydrogenated methylene dianiline) and 3 , 9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane and the like} and a heterocyclic diamine having 4 to 15 carbon atoms [piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine, 1,4-bis (2-amino-2-methylpropyl) piperazine, etc.] and the like.

  The aromatic diamine having 6 to 20 carbon atoms is an aromatic having an unsubstituted aromatic diamine or an alkyl group (an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n- or isopropyl group, and a butyl group). Examples include diamines.

  Examples of the unsubstituted aromatic diamine include 1,2-, 1,3- or 1,4-phenylenediamine, 2,4′- or 4,4′-diphenylmethanediamine, diaminodiphenylsulfone, benzidine, thiodianiline, bis (3 , 4-diaminophenyl) sulfone, 2,6-diaminopyridine, m-aminobenzylamine, naphthylenediamine and mixtures thereof.

  Examples of the aromatic diamine having an alkyl group include 2,4- or 2,6-tolylenediamine, crude tolylenediamine, diethyltolylenediamine, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 4'-bis (o-toluidine), dianisidine, diaminoditolyl sulfone, 1,3-dimethyl-2,4-diaminobenzene, 1,3-diethyl-2,4-diaminobenzene, 1,3-dimethyl-2 , 6-diaminobenzene, 1,4-diethyl-, 2,5-diaminobenzene, 1,4-diisopropyl-2,5-diaminobenzene, 1,4-dibutyl-2,5-diaminobenzene, 2,4- Diaminomesitylene, 1,3,5-triethyl-2,4-diaminobenzene, 1,3,5-triisopropyl-2,4-diaminobenzene 1-methyl-3,5-diethyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene, 2,3-dimethyl-1,4-diaminonaphthalene, 2,6 -Dimethyl-1,5-diaminonaphthalene, 2,6-diisopropyl-1,5-diaminonaphthalene, 2,6-dibutyl-1,5-diaminonaphthalene, 3,3 ', 5,5'-tetramethylbenzidine, 3,3 ′, 5,5′-tetraisopropylbenzidine, 3,3 ′, 5,5′-tetramethyl-4,4′-diaminodiphenylmethane, 3,3 ′, 5,5′-tetraethyl-4,4 '-Diaminodiphenylmethane, 3,3', 5,5'-tetraisopropyl-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetrabutyl-4,4'-diamino Phenylmethane, 3,5-diethyl-3′-methyl-2 ′, 4-diaminodiphenylmethane, 3,5-diisopropyl-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 ′ -Tetraisopropyl-4,4'-diaminobenzophenone, 3,3 ', 5,5'-tetraethyl-4,4'-diaminodiphenyl ether, 3,3', 5,5'-tetraisopropyl-4,4'- Examples thereof include diaminodiphenyl sulfone and a mixture thereof.

  As the diisocyanate (4), an aromatic diisocyanate having 6 to 20 carbon atoms (excluding carbon in the NCO group; the same shall apply hereinafter), an aliphatic diisocyanate having 2 to 18 carbon atoms, a chain aliphatic diisocyanate, and an alicyclic diisocyanate. , Modified products of these diisocyanates (urethane groups, carbodiimide groups, allophanate groups, urea groups, burette groups, uretdione groups, uretoimine groups, isocyanurate groups and oxazolidone group-containing modified products) and mixtures of two or more of these Is mentioned.

  Aromatic diisocyanates include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), crude TDI, m- or p-xylylene diisocyanate (XDI), α , Α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI), 2,4′- or 4,4′-diphenylmethane diisocyanate (MDI), crude MDI {crude diaminophenylmethane [formaldehyde and aromatic amine (aniline) ) Or a mixture thereof and a mixture thereof.

Examples of the aliphatic diisocyanate include a chain aliphatic diisocyanate and a cyclic aliphatic diisocyanate.
Examples of chain aliphatic diisocyanates include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and 2,6-diisocyanatomethylcaproate. Bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate, and mixtures thereof.

  Examples of alicyclic diisocyanates include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), and bis (2-isocyanatoethyl). -4-cyclohexene-1,2-dicarboxylate, 2,5- or 2,6-norbornane diisocyanate, and mixtures thereof.

As a modified product of diisocyanate, a modified product containing a urethane group, a carbodiimide group, an allophanate group, a urea group, a burette group, a uretdione group, a uretoimine group, an isocyanurate group and / or an oxazolidone group is used. Urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI, etc.), urethane-modified TDI, and mixtures thereof (for example, a mixture of modified MDI and urethane-modified TDI (isocyanate-containing prepolymer)).
Of these modified products, a polyisocyanate component having three or more functional groups can also be used.

  Of the diisocyanates (4), aromatic diisocyanates having 6 to 15 carbon atoms and aliphatic diisocyanates having 4 to 15 carbon atoms are preferred, and TDI, MDI, HDI, hydrogenated MDI and IPDI are more preferred. .

The crystalline polyurethane resin (A2) is selected from the group consisting of a carboxylic acid (salt) group, a sulfonic acid (salt) group, a sulfamic acid (salt) group, and a phosphoric acid (salt) group in addition to the diol (1). A diol (1 ′) having at least one group may be a structural unit. When (A2) uses the diol (1 ′) as a structural unit, the chargeability and heat-resistant storage stability of the resin particles are improved.
The “acid (salt)” in the present invention means an acid or an acid salt.

Examples of the diol (1 ′) having a carboxylic acid (salt) group include tartaric acid (salt), 2,2-bis (hydroxymethyl) propanoic acid (salt), and 2,2-bis (hydroxymethyl) butanoic acid (salt). And 3- [bis (2-hydroxyethyl) amino] propanoic acid (salt) and the like.
Examples of the diol (1 ′) having a sulfonic acid (salt) group include 2,2-bis (hydroxymethyl) ethanesulfonic acid (salt) and 2- [bis (2-hydroxyethyl) amino] ethanesulfonic acid (salt). And 5-sulfo-isophthalic acid-1,3-bis (2-hydroxyethyl) ester (salt) and the like.
Examples of the diol (1 ′) having a sulfamic acid (salt) group include N, N-bis (2-hydroxyethyl) sulfamic acid (salt), N, N-bis (3-hydroxypropyl) sulfamic acid (salt), Examples thereof include N, N-bis (4-hydroxybutyl) sulfamic acid (salt) and N, N-bis (2-hydroxypropyl) sulfamic acid (salt).
Examples of the diol (1 ′) having a phosphoric acid (salt) group include bis (2-hydroxyethyl) phosphate (salt).
The salts that make up the acid salts include ammonium salts, amine salts (methylamine salts, dimethylamine salts, trimethylamine salts, ethylamine salts, diethylamine salts, triethylamine salts, propylamine salts, dipropylamine salts, tripropylamine salts, butylamines. Salt, dibutylamine salt, tributylamine salt, monoethanolamine salt, diethanolamine salt, triethanolamine salt, N-methylethanolamine salt, N-ethylethanolamine salt, N, N-dimethylethanolamine salt, N, N- Diethylethanolamine salt, hydroxylamine salt, N, N-diethylhydroxylamine salt, morpholine salt, etc.), quaternary ammonium salt [tetramethylammonium salt, tetraethylammonium salt and trimethyl (2-hydroxyethyl) Ammonium salts, alkali metal salts (sodium salts and potassium salts, etc.).
Among the diols (1 ′), the diol (1 ′) having a carboxylic acid (salt) group and the diol (1) having a sulfonic acid (salt) group are preferable from the viewpoint of chargeability of the resin particles and heat-resistant storage stability. ').

Examples of the crystalline polyurea resin (A3) include those having the diamine (3) and the diisocyanate (4) as structural units.

Examples of the crystalline polyamide resin (A4) include those having the dicarboxylic acid (2) and the diamine (3) as structural units.

The crystalline vinyl resin (A5) is a polymer obtained by homopolymerizing or copolymerizing a monomer having a polymerizable double bond. Examples of the monomer having a polymerizable double bond include the following (5) to (13).

(5) Hydrocarbon having a polymerizable double bond:
(5-1) Aliphatic hydrocarbon having a polymerizable double bond:
(5-1-1) Chain hydrocarbon having a polymerizable double bond: Alkene having 2 to 30 carbon atoms (for example, ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, etc.) An alkadiene having 4 to 30 carbon atoms (for example, butadiene, isoprene, 1,4-pentadiene, 1,5-hexadiene, 1,7-octadiene, etc.);
(5-1-2) Cyclic hydrocarbon having a polymerizable double bond: mono- or dicycloalkene having 6 to 30 carbon atoms (for example, cyclohexene, vinylcyclohexene and ethylidenebicycloheptene) and mono-carbon having 5 to 30 carbon atoms Or dicycloalkadiene [for example, (di) cyclopentadiene etc.] etc.
(5-2) Aromatic hydrocarbons having a polymerizable double bond: styrene; hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl having 1 to 30 carbon atoms) substituted styrene (for example, α-methylstyrene) Vinyl toluene, 2,4-dimethylstyrene, ethyl styrene, isopropyl styrene, butyl styrene, phenyl styrene, cyclohexyl styrene, benzyl styrene, crotyl benzene, divinyl benzene, divinyl toluene, divinyl xylene, and trivinyl benzene); and vinyl Naphthalene etc.

(6) Monomers having a carboxyl group and a polymerizable double bond and their salts:
C3-C15 unsaturated monocarboxylic acid {For example, (meth) acrylic acid ["(meth) acryl" means acryl or methacryl. ], Crotonic acid, isocrotonic acid, cinnamic acid and the like}; C3-C30 unsaturated dicarboxylic acid (anhydride) [for example, (anhydrous) maleic acid, fumaric acid, itaconic acid, (anhydrous) citraconic acid, mesaconic acid, etc. And monoalkyl (C1-10) esters of unsaturated dicarboxylic acids having 3 to 10 carbon atoms (eg maleic acid monomethyl ester, maleic acid monodecyl ester, fumaric acid monoethyl ester, itaconic acid monobutyl ester and citracone) Acid monodecyl ester, etc.).
Examples of the salt constituting the monomer salt having a carboxyl group and a polymerizable double bond include alkali metal salts (such as sodium salt and potassium salt), alkaline earth metal salts (such as calcium salt and magnesium salt), and ammonium. Examples thereof include salts, amine salts, and quaternary ammonium salts.
The amine salt is not particularly limited as long as it is an amine compound. For example, primary amine salts (such as ethylamine salts, butylamine salts and octylamine salts), secondary amines (such as diethylamine salts and dibutylamine salts), tertiary amines ( Triethylamine salt and tributylamine salt). Examples of the quaternary ammonium salt include tetraethylammonium salt, triethyllaurylammonium salt, tetrabutylammonium salt, and tributyllaurylammonium salt.
Examples of the salt of the monomer having a carboxyl group and a polymerizable double bond include sodium acrylate, sodium methacrylate, monosodium maleate, disodium maleate, potassium acrylate, potassium methacrylate, monopotassium maleate, acrylic Examples include lithium acid, cesium acrylate, ammonium acrylate, calcium acrylate, and aluminum acrylate.

(7) Monomers having a sulfo group and a polymerizable double bond and their salts:
Alkene sulfonic acids having 2 to 14 carbon atoms (for example, vinyl sulfonic acid, (meth) allyl sulfonic acid and methyl vinyl sulfonic acid); styrene sulfonic acid and alkyl (2 to 24 carbon) derivatives thereof (for example, α-methyl styrene sulfone) Acid etc .; C5-C18 sulfo (hydroxy) alkyl- (meth) acrylate (for example, sulfopropyl (meth) acrylate, 2-hydroxy-3- (meth) acryloxypropylsulfonic acid, 2- (meth) acryloyloxy) Ethanesulfonic acid and 3- (meth) acryloyloxy-2-hydroxypropanesulfonic acid); sulfo (hydroxy) alkyl (meth) acrylamide having 5 to 18 carbon atoms [eg 2- (meth) acryloylamino-2,2- Dimethylethanesulfonic acid, 2- (meth) acrylic Do-2-methylpropanesulfonic acid and 3- (meth) acrylamide-2-hydroxypropanesulfonic acid, etc.]; alkyl (C3-C18) allylsulfosuccinic acid (for example, propylallylsulfosuccinic acid, butylallylsulfosuccinic acid, 2- Ethylhexyl-allylsulfosuccinic acid, etc.); poly [n (degree of polymerization, the same applies hereinafter) = 2-30] oxyalkylene (oxyethylene, oxypropylene, oxybutylene, etc.). Oxyalkylene may be used alone or in combination. The addition type may be random addition or block addition.) Sulfate ester of mono (meth) acrylate [for example, poly (n = 5-15) oxyethylene monomethacrylate sulfate and poly (n = 5-15) oxypropylene monomethacrylate sulfate Esters etc.]; Compounds represented by the general formulas (1) to (3); and salts thereof.
In addition, as a salt, what was illustrated as a salt which comprises the salt of the monomer which has (6) a carboxyl group and a polymerizable double bond is mentioned.

In Formulas (1) to (3), R ¹ is an alkylene group having 2 to 4 carbon atoms, and when there are a plurality of R ¹ Os, one or two or more types may be used, and when two or more types are used in combination, The combination form may be random or block. R ² and R ³ are each independently an alkyl group having 1 to 15 carbon atoms; m and n are each independently a number of 1 to 50; Ar is a benzene ring; R ⁴ may be substituted with a fluorine atom A good alkyl group having 1 to 15 carbon atoms is represented.

(8) Monomer having phosphono group and polymerizable double bond and salt thereof:
(Meth) acryloyloxyalkyl phosphate monoester (alkyl group having 1 to 24 carbon atoms) (for example, 2-hydroxyethyl (meth) acryloyl phosphate and phenyl-2-acryloyloxyethyl phosphate), (meth) acryloyloxyalkyl Phosphonic acid (alkyl group having 1 to 24 carbon atoms) (for example, 2-acryloyloxyethylphosphonic acid).
In addition, as a salt, what was illustrated as a salt which comprises the monomer which has (6) carboxyl group and a polymerizable double bond is mentioned.

(9) Monomer having a hydroxyl group and a polymerizable double bond:
Hydroxystyrene, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, (meth) allyl alcohol, crotyl alcohol, isocrotyl alcohol, 1- Buten-3-ol, 2-buten-1-ol, 2-butene-1,4-diol, propargyl alcohol, 2-hydroxyethylpropenyl ether, sucrose allyl ether, and the like.

(10) Nitrogen-containing monomer having a polymerizable double bond:
(10-1) Monomer having amino group and polymerizable double bond:
Aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, t-butylaminoethyl methacrylate, N-aminoethyl (meth) acrylamide, (meth) allylamine, morpholinoethyl (meth) acrylate, 4-vinylpyridine, 2-vinylpyridine, crotylamine, N, N-dimethylaminostyrene, methyl-α-acetaminoacrylate, vinylimidazole, N-vinylpyrrole, N-vinylthiopyrrolidone, N-arylphenylenediamine, aminocarbazole , Aminothiazole, aminoindole, aminopyrrole, aminoimidazole, aminomercaptothiazole and salts thereof.
(10-2) Monomer having amide group and polymerizable double bond:
(Meth) acrylamide, N-methyl (meth) acrylamide, N-butyl acrylamide, diacetone acrylamide, N-methylol (meth) acrylamide, N, N′-methylene-bis (meth) acrylamide, cinnamic amide, N, N -Dimethylacrylamide, N, N-dibenzylacrylamide, methacrylformamide, N-methyl-N-vinylacetamide, N-vinylpyrrolidone and the like.
(10-3) A monomer having 3 to 10 carbon atoms having a nitrile group and a polymerizable double bond:
(Meth) acrylonitrile, cyanostyrene, cyanoacrylate and the like.
(10-4) Monomers having 8 to 12 carbon atoms having a nitro group and a polymerizable double bond:
Nitrostyrene etc.

(11) A monomer having 6 to 18 carbon atoms having an epoxy group and a polymerizable double bond:
Glycidyl (meth) acrylate and p-vinylphenylphenyl oxide.

(12) A monomer having 2 to 16 carbon atoms having a halogen element and a polymerizable double bond:
Vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride, chlorostyrene, bromostyrene, dichlorostyrene, chloromethylstyrene, tetrafluorostyrene, chloroprene and the like.

(13) An ester having a polymerizable double bond, an ether having a polymerizable double bond, a ketone having a polymerizable double bond, and a sulfur-containing compound having a polymerizable double bond:
(13-1) C4-16 ester having a polymerizable double bond:
Vinyl acetate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl methacrylate, methyl-4-vinyl benzoate, cyclohexyl methacrylate, benzyl methacrylate, phenyl (meth) acrylate, vinyl methoxyacetate, vinyl benzoate, ethyl -Α-ethoxy acrylate, (meth) acrylic acid ester having 1 to 50 carbon atoms [methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate and eicosyl (meth) acrylate Rate, etc.], dialkyl fumarate (two alkyl groups are straight, branched or alicyclic groups having 2 to 8 carbon atoms), dialkyl maleate (two alkyl groups are carbon atoms 2-8 linear, branched or alicyclic groups), poly (meth) allyloxyalkanes (diallyloxyethane, triaryloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetra Monomers having a polyalkylene glycol chain and a polymerizable double bond [polyethylene glycol [Mn = 300] mono (meth) acrylate, polypropylene glycol (Mn = 500) mono), such as allyloxybutane and tetrametaallyloxyethane) Acrylate, methyl alcohol EO 10 mol adduct (meth) acrylate and lauryl alcohol EO 30 mol adduct (meth) a Acrylates, etc.], poly (meth) acrylates [poly (meth) acrylates of polyhydric alcohols: ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane] Tri (meth) acrylate and polyethylene glycol di (meth) acrylate, etc.].

(13-2) C3-C16 ether having a polymerizable double bond:
Vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl butyl ether, vinyl-2-ethylhexyl ether, vinyl phenyl ether, vinyl-2-methoxyethyl ether, methoxybutadiene, vinyl-2-butoxyethyl ether, 3,4-dihydro -1,2-pyran, 2-butoxy-2′-vinyloxydiethyl ether, acetoxystyrene, phenoxystyrene, and the like.
(13-3) C4-C12 ketone having a polymerizable double bond:
Examples include vinyl methyl ketone, vinyl ethyl ketone, and vinyl phenyl ketone.
(13-4) C2-C16 sulfur-containing compound having a polymerizable double bond:
Examples thereof include divinyl sulfide, p-vinyl diphenyl sulfide, vinyl ethyl sulfide, vinyl ethyl sulfone, divinyl sulfone, and divinyl sulfoxide.

  Examples of the crystalline epoxy resin (A6) include a ring-opening polymer of polyepoxide (14), polyepoxide (14) and active hydrogen-containing compound [water, diol (1), dicarboxylic acid (2), diamine (3), etc.] And polyaddition products.

  The polyepoxide (14) is not particularly limited as long as it has two or more epoxy groups in the molecule. Of the polyepoxides (14), those having 2 to 6 epoxy groups in the molecule are preferred from the viewpoint of the mechanical properties of the cured product. The epoxy equivalent (molecular weight per epoxy group) of the polyepoxide (14) is preferably 65 to 1,000, and more preferably 90 to 500. When the epoxy equivalent is 1,000 or less, the cross-linked structure becomes dense and physical properties such as water resistance, chemical resistance and mechanical strength of the cured product are improved. On the other hand, those having an epoxy equivalent of less than 65 are synthesized. It is difficult.

Examples of the polyepoxide (14) include aromatic polyepoxy compounds, heterocyclic polyepoxy compounds, alicyclic polyepoxy compounds, and aliphatic polyepoxy compounds.
Examples of the aromatic polyepoxy compounds include glycidyl ethers and glycidyl ethers of polyhydric phenols, glycidyl aromatic polyamines, and glycidylates of aminophenols.

Examples of glycidyl ethers of polyphenols include bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol B diglycidyl ether, bisphenol AD diglycidyl ether, bisphenol S diglycidyl ether, halogenated bisphenol A diglycidyl, and tetrachlorobisphenol A. Diglycidyl ether, catechin diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, pyrogallol triglycidyl ether, 1,5-dihydroxynaphthalene diglycidyl ether, dihydroxybiphenyl diglycidyl ether, octachloro-4,4'-dihydroxybiphenyldi Glycidyl ether, tetramethylbiphenyl diglycidyl ester Ter, dihydroxynaphthylcresol triglycidyl ether, tris (hydroxyphenyl) methane triglycidyl ether, dinaphthyltriol triglycidyl ether, tetrakis (4-hydroxyphenyl) ethanetetraglycidyl ether, p-glycidylphenyldimethyltolylbisphenol A glycidyl ether, trismethyl -T-butyl-butylhydroxymethane triglycidyl ether, 9,9'-bis (4-hydroxyphenyl) furorange glycidyl ether, 4,4'-oxybis (1,4-phenylethyl) tetracresol glycidyl ether, 4 , 4′-oxybis (1,4-phenylethyl) phenylglycidyl ether, bis (dihydroxynaphthalene) tetraglycidyl ether, phenol Or cresol novolak resin glycidyl ether, limonene phenol novolak resin glycidyl ether, diglycidyl ether obtained from the reaction of 2 mol of bisphenol A and 3 mol of epichlorohydrin, condensation of phenol and glyoxal, glutaraldehyde or formaldehyde Examples thereof include polyglycidyl ethers of polyphenols obtained by the reaction and polyglycidyl ethers of polyphenols obtained by the condensation reaction of resorcin and acetone.

Examples of the glycidyl ester of polyhydric phenol include phthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, and terephthalic acid diglycidyl ester.
Examples of the glycidyl aromatic polyamine include N, N-diglycidylaniline, N, N, N ′, N′-tetraglycidylxylylenediamine and N, N, N ′, N′-tetraglycidyldiphenylmethanediamine. Furthermore, as the aromatic system, triglycidyl ether of p-aminophenol, tolylene diisocyanate or diglycidyl urethane compound obtained by addition reaction of diphenylmethane diisocyanate and glycidol, glycidyl group obtained by reacting polyol with the two reactants Also included is a diglycidyl ether of an AO adduct of bisphenol A and a containing polyurethane (pre) polymer.

Examples of the heterocyclic polyepoxy compound include trisglycidylmelamine.
Examples of the alicyclic polyepoxy compound include vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl) ether, ethylene glycol bisepoxy dicyclopentyl ale, 3,4-epoxy- 6-methylcyclohexylmethyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexyl) Methyl) butylamine and dimer acid diglycidyl ester. The alicyclic group also includes a nuclear hydrogenated product of the aromatic polyepoxide compound.

Examples of the aliphatic polyepoxy compound include polyglycidyl ethers of polyhydric aliphatic alcohols, polyglycidyl esters of polyhydric fatty acids, and glycidyl aliphatic amines. Polyglycidyl ethers of polyhydric aliphatic alcohols include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol Examples include diglycidyl ether, polytetramethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether and polyglycerol polyglycidyl ether. It is done. Examples of polyglycidyl ester of polyvalent fatty acid include diglycidyl oxalate, diglycidyl malate, diglycidyl succinate, diglycidyl glutarate, diglycidyl adipate and diglycidyl pimelate. Examples of the glycidyl aliphatic amine include N, N, N ′, N′-tetraglycidylhexamethylenediamine. As the aliphatic group, a (co) polymer of diglycidyl ether and glycidyl (meth) acrylate is also included.
Of the polyepoxides (14), aliphatic polyepoxy compounds and aromatic polyepoxy compounds are preferred. Two or more polyepoxides may be used in combination.

Examples of the crystalline polyether resin (A7) include crystalline polyoxyalkylene polyols.
The method for producing the crystalline polyoxyalkylene polyol is not particularly limited, and any known method may be used.

For example, a method in which a chiral polyoxyalkylene polyol is subjected to ring-opening polymerization using a catalyst used in ordinary polyoxyalkylene polyol polymerization (Journal of the American Chemical Society, 1956, Vol. 78, No. 18, p. 4787-4792) and an inexpensive racemic polyoxyalkylene polyol by ring-opening polymerization using a sterically bulky complex having a special chemical structure as a catalyst.
As a method using a special complex, a method in which a compound obtained by contacting a lanthanoid complex with organoaluminum is used as a catalyst (described in JP-A-11-12353), or bimetal-μ-oxoalkoxide and a hydroxyl compound are reacted in advance. And the like (described in JP 2001-521957 A).

In addition, as a method for obtaining a polyoxyalkylene polyol having very high isotacticity, a method using a salen complex as a catalyst (Journal of the American Chemical Society, 2005, Vol. 127, No. 33, p. 11566-11567) Description) and the like.

For example, when a chiral polyoxyalkylene polyol is used and glycol or water is used as an initiator during the ring-opening polymerization, a polyoxyalkylene glycol having a hydroxyl group at the terminal and having an isotacticity of 50% or more is obtained. It is done. The polyoxyalkylene glycol having an isotacticity of 50% or more may be modified such that its terminal is, for example, a carboxyl group. If the isotacticity is 50% or more, the polyoxyalkylene polyol usually has crystallinity.
Examples of the glycol include the diol (1), and examples of the carboxylic acid used for carboxy modification include the dicarboxylic acid (2).

The raw materials used for the production of the crystalline polyoxyalkylene polyol include PO, 1-chlorooxetane, 2-chlorooxetane, 1,2-dichlorooxetane, epichlorohydrin, epibromohydrin, BO, methyl glycidyl ether, 1 , 2-pentylene oxide, 2,3-pentylene oxide, 3-methyl-1,2-butylene oxide, cyclohexene oxide, 1,2-hexylene oxide, 3-methyl-1,2-pentylene oxide, 2 , 3-hexylene oxide, 4-methyl-2,3-pentylene oxide, allyl glycidyl ether, 1,2-heptylene oxide, styrene oxide, phenyl glycidyl ether, and the like. These raw materials may be used alone or in combination of two or more. Of these, PO, BO, styrene oxide, and cyclohexene oxide are preferable.

Of the crystalline resins (A), the crystalline polyester resin (A1), the crystalline polyurethane resin (A2), the crystalline polyurea resin (A3), and the crystalline polyamide resin (A4) are preferable from the viewpoint of low-temperature fixability. More preferred is a crystalline resin having at least one functional group selected from the group consisting of an ester group, a urethane group, a urea group and an amide group, and particularly preferred is a crystal having an ester group. Resin.

In the case where the crystalline resin (A) has an ester group, the ester group concentration of (A) based on the weight of (A) is preferably 5 to 75 weights from the viewpoint of heat-resistant storage stability and wet heat-resistant storage stability. %, More preferably 10 to 70% by weight, particularly preferably 15 to 65% by weight, and most preferably 20 to 60% by weight.
The ester group concentration based on the weight of (A) of the crystalline resin (A) can be calculated from the number of ester groups [—C (═O) O—] in (A).

The Ta of the crystalline resin (A) is preferably 50 to 100 ° C., more preferably 55 to 95 ° C., and particularly preferably 60 to 90 ° C. from the viewpoint of low-temperature fixability of the toner (Z).
In addition, as (A), you may contain 2 or more types (A) from which Ta differs.

  The acid value of the crystalline resin (A) is preferably 30 mgKOH / g or less, more preferably 25 mgKOH / g, and particularly preferably 20 mgKOH / g or less from the viewpoints of heat-resistant and wet heat-resistant storage.

  The Mw of the crystalline resin (A) is preferably 3,000 to 50,000, more preferably 3 from the viewpoint of achieving both low-temperature fixability, heat-resistant storage stability and wet heat-resistant storage stability of the toner (Z). , 500 to 35,000, particularly preferably 4,000 to 25,000.

  The molecular weight distribution obtained by gel permeation chromatography of the crystalline resin (A) is a molecular weight of 3,000 to 50,000 from the viewpoint of compatibility between the low-temperature fixability of toner (Z) and the heat and heat and heat resistance. Preferably having at least one peak in the region of molecular weight, more preferably having at least one peak in the region of molecular weight 3,500-35,000, and at least one peak in the region of molecular weight 4,000-25,000. It is particularly preferred to have

Mn and Mw of the resin in the present invention can be measured under the following conditions using gel permeation chromatography (GPC).
Apparatus (example): “HLC-8120” [manufactured by Tosoh Corporation]
Column (example): “TSK GEL GMH6” [manufactured by Tosoh Corporation] Measurement temperature: 40 ° C.
Sample solution: 0.25% by weight tetrahydrofuran solution (insoluble matter filtered off with glass filter)
Solution injection volume: 100 μl
Detection apparatus: Refractive index detector Reference material: Standard polystyrene (TSK standard POLYSTYRENE) 12 points (Molecular weight: 500, 1,050, 2,800, 5,970, 9,100,
18,100,37,900,96,400,190,000,355,000,
1,090,000, 2,890,000) [manufactured by Tosoh Corporation]

The crystalline resin (A) preferably satisfies [Condition 2] and [Condition 3] simultaneously from the viewpoint of low-temperature fixability.
[Condition 2]
G ′ (Ta + 10) ≦ 1,000 [Pa · s]
However, G ′ (Ta + 10) represents the storage elastic modulus [Pa · s] of (A) at (Ta + 10) [° C.].

[Condition 3]
1 × 10 ⁶ ≦ G ′ (Ta−10) ≦ 1 × 10 ⁹ [Pa · s]
However, G ′ (Ta-10) represents the storage elastic modulus [Pa · s] of (A) at (Ta-10) [° C.].

The G ′ (Ta + 10) value on the left side of Condition 2 is preferably 800 or less.
Further, the value of G ′ (Ta−10) in the center of Condition 3 is preferably 1 × 10 ⁸ Pa · s or less.

The storage elastic modulus G ′ in the present invention can be measured under the following conditions.
Apparatus: ARES-24A (Rheometric)
Jig: 8mm parallel plate Frequency: 1Hz
Distortion rate: 1%
Temperature increase rate: 3 ° C / min

The solubility parameter (hereinafter abbreviated as SP value) of the crystalline resin (A) is preferably 9.0 to 12.0 (cal / cm ³ ) ^1/2 from the viewpoint of compatibility with the vinyl resin. More preferably, it is 9.5 to 11.5 (cal / cm ³ ) ^1/2 , and particularly preferably 9.5 to 11.0 (cal / cm ³ ) ^1/2 .
In addition, SP value in this invention is the method by Fedors [Polym. Eng. Sci. 14 (2) 152, (1974)].

The crystalline resin (A) preferably satisfies [Condition 4] from the viewpoint of low-temperature fixability and gloss.
[Condition 4]
3 ≦ Log {G ′ (Ta−10)} − Log {G ′ (Ta + 10)} ≦ 8
However, G ′ (Ta-10) is the storage elastic modulus [Pa · s] of (A) at (Ta-10) [° C.], and G ′ (Ta + 10) is that of (A) at (Ta + 10) [° C.]. The storage elastic modulus [Pa · s] is represented.
The value of Log {G ′ (Ta−10)} − Log {G ′ (Ta + 10)} in Condition 4 is more preferably 3 or more and 7 or less.

The crystalline resin (A) satisfying [Condition 2], [Condition 3], and [Condition 4] is obtained by adjusting the SP value of the crystalline component in (A), adjusting the weight average molecular weight, and the like. be able to.
For example, in the molecular weight distribution obtained by gel permeation chromatography, increasing the ratio of the crystalline part having a peak in the low molecular weight region decreases the value of G ′ (Ta + 10). Further, the value of G ′ (Ta + 10) is decreased by decreasing the SP value of (A).

As the vinyl resin (B) having an ester group in the present invention, “(13-1) carbon number 4 to 16 having a polymerizable double bond” exemplified as a constituent monomer of the crystalline vinyl resin (A5). Vinyl ester having “ester” as a constituent monomer.
From the viewpoint of low-temperature fixability, (B) is preferably a vinyl resin having (meth) acrylic acid ester having a C 1-50 alkyl group as a structural unit.

The vinyl resin (B) having an ester group is a constituent monomer of the crystalline vinyl resin (A5) in addition to “(13-1) an ester having 4 to 16 carbon atoms having a polymerizable double bond”. A vinyl resin having a monomer arbitrarily selected from the exemplified (5) to (13) is also preferred.
From the viewpoint of compatibility with the crystalline resin (A), an ester having an aromatic hydrocarbon having a polymerizable double bond and / or an unsaturated monocarboxylic acid having 3 to 15 carbon atoms as a structural unit is more preferable. Vinyl resin having a group.
(B) may be used alone or in combination of two or more.

  The Mw of the vinyl resin (B) having an ester group is preferably from 3,000 to 2,500,000, more preferably from 3,500, from the viewpoints of low-temperature fixability, heat-resistant storage stability, wet heat storage resistance and durability. 2 million, particularly preferably 4,000 to 1.8 million.

In the molecular weight distribution obtained by gel permeation chromatography, the vinyl resin (B) having an ester group in the present invention has at least a molecular weight of 3,000 to 60,000 only from the viewpoint of low-temperature fixability of the toner (Z). It may have one peak.

In addition, the vinyl resin (B) having an ester group may be used alone or in combination of two or more. In the molecular weight distribution obtained by gel permeation chromatography, low temperature fixability, heat resistant storage stability, moisture heat storage resistance and durability. From the standpoint of compatibility, it is preferable that each has at least one peak in a region having a molecular weight of 3,000 to 60,000 and a region having a molecular weight of 100,000 to 2.5 million.
More preferred are those having at least one peak in the 3,500 to 40,000 region and 120,000 to 2 million region, respectively, and particularly preferred are the 4,000 to 20,000 region. , Each having at least one peak in the region of 140,000 to 1.8 million.

The vinyl resin (B) having an ester group has a molecular weight of 10 and a resin (LB) having at least one peak in a molecular weight region of 3,000 to 60,000 in the molecular weight distribution obtained by gel permeation chromatography. It may be a resin (HB) mixture having at least one peak in the range of 10,000 to 2.5 million.
When (B) is a mixture of (LB) and (HB), (LB) and (HB) may be combined at once, or (LB) and (HB) may be combined and mixed. Good.
Examples of the method of mixing (LB) and (HB) include powder mixing, melt kneading, and dissolution mixing.

The Mw of (LB) is preferably from 3,000 to 60,000, more preferably from 3,500 to 40,000, particularly preferably from 4,000 to 20 from the viewpoint of low-temperature fixability of the toner (Z). , 000.

The Mw of (HB) is preferably 100,000 to 2,500,000, more preferably 120,000 to 2,000,000, particularly preferably, from the viewpoints of heat resistant storage stability, wet heat storage resistance and durability improvement of the toner (Z). 140,000 to 1.8 million.

The acid value of the vinyl resin (B) having an ester group is preferably 30 mgKOH / g or less, more preferably 25 mgKOH / g, particularly preferably 20 mgKOH, from the viewpoints of heat resistance and heat and heat resistance of the toner (Z). / G.

The glass transition temperature (hereinafter abbreviated as Tg) of the vinyl resin (B) having an ester group is preferably 40 to 110 ° C., more preferably 40 to 100 ° C., particularly from the viewpoint of low-temperature fixability of the toner (Z). Preferably it is 40-90 degreeC.

The vinyl resin (B) having an ester group can be obtained by a known polymerization method such as solution polymerization, bulk polymerization, suspension polymerization and emulsion polymerization using the monomer and the radical polymerization initiator.
Among these polymerization methods, preferred from the viewpoint of molecular weight control are solution polymerization, suspension polymerization, bulk polymerization, and combinations thereof.
Examples of the radical initiator include azo polymerization initiators (for example, azobisisobutyronitrile, azobisvaleronitrile, and azobiscyanovaleric acid), and organic peroxide polymerization initiators [for example, benzoyl peroxide, di-t- Butyl peroxide, t-butyl peroxybenzoate, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane] and the like.
Of these, di-t-butyl peroxide and 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane are preferred.
The amount of the polymerization initiator used is preferably 0.01 to 10% by weight, more preferably 0.05 to 8% by weight, and particularly preferably 0.1 to 6% by weight, based on the total amount of monomers.

Examples of the organic solvent that can be used for the synthesis of the vinyl resin (B) having an ester group of the present invention include aromatic hydrocarbon solvents (toluene, xylene, ethylbenzene, tetralin, etc.); aliphatic hydrocarbon solvents (n-hexane, n -Heptane, n-decane, mineral spirits and cyclohexane, etc .; Halogen solvents (such as methyl chloride, methyl bromide, methyl iodide, methylene dichloride, carbon tetrachloride, trichloroethylene and perchloroethylene); Ester solvents (ethyl acetate, acetic acid, etc.) Butyl, methyl 2-hydroxyisobutyrate, methyl lactate, ethyl lactate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, methyl pyruvate and ethyl pyruvate); ether solvents (diethyl ether, tetrahydrofuran, dioxane, Oxolane, ethyl cellosolve, butyl cellosolve, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether, etc .; ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, cyclohexanone, etc.) Alcohol solvent (methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2-ethylhexyl alcohol, benzyl alcohol, 2,2,3,3-tetrafluoropropanol, trifluoroethanol, etc.) ); Amide solvents (dimethylformamide, dimethylacetamide, etc.); Sulfoxide solvents (dimethylsulfone) Sid, etc.); heterocyclic compounds solvents (N- methylpyrrolidone) and include mixed solvent of two or more thereof.
Of these, aromatic solvents are preferable from the viewpoint of operability, and xylene, toluene, and ethylbenzene are more preferable.
Moreover, when performing suspension polymerization, it can superpose | polymerize in water using the below-mentioned inorganic dispersing agent, a water-soluble polymer, etc.

The content of the styrene monomer in the toner (Z) obtained by the production method of the present invention is preferably 100 ppm or less based on the weight of (Z) from the viewpoints of heat resistant storage stability, wet heat storage resistance and durability. More preferably 50 ppm or less, particularly preferably 25 ppm or less, and most preferably 5 ppm or less. The monomer content in (Z) can be measured by gas chromatography.

The monomer content in the toner (Z) obtained by the production method of the present invention is preferably 300 ppm or less, based on the weight of (Z), from the viewpoints of heat-resistant storage stability, moisture-heat storage resistance and durability. More preferably, it is 200 ppm or less, particularly preferably 100 ppm or less, and most preferably 50 ppm or less. The monomer content in (Z) can be measured by gas chromatography.

An example of measurement conditions for measuring the monomer content and the styrene monomer content in the toner (Z) by gas chromatography is shown below.
Model: “GC2010” [manufactured by Shimadzu Corporation]
Column: “DB-5” (5 wt% phenylmethylpolysiloxane, inner diameter 0.25 mm, length 30 m) [manufactured by Shimadzu Corporation]
Eluent: Dimethylformamide Flow rate: 40.5 ml / min
Detector temperature: 250 ° C
Injection volume: 1 μl

The content of the volatile organic compound (hereinafter abbreviated as VOC) in the toner (Z) obtained by the production method of the present invention is the same as that of (Z) from the viewpoints of heat-resistant storage, wet heat storage and durability. Based on the weight, it is preferably 500 ppm or less, more preferably 300 ppm or less, particularly preferably 200 ppm or less, and most preferably 100 ppm or less. The content of VOC in (Z) can be measured by gas chromatography.

A certain amount of toner (Z) is heated at 130 ° C. for a certain period of time, the generated VOC gas is collected, and the content of VOC in (Z) is measured by gas chromatography. An example of measurement conditions is shown below.
Model: “GC2010” [manufactured by Shimadzu Corporation]
Column: “DB-5” (5 wt% phenylmethylpolysiloxane, inner diameter 0.25 mm, length 30 m) [manufactured by Shimadzu Corporation]
Flow rate: 40.5 ml / min
Detector temperature: 250 ° C
Injection volume: 1 μl

The ester group concentration based on the weight of (B) of the vinyl resin (B) having an ester group is preferably 5 to 60% by weight, more preferably 10 to 55% by weight, particularly from the viewpoint of low-temperature fixability. Preferably it is 15-50 weight%, Most preferably, it is 20-45 weight%.
The ester group concentration based on the weight of (B) in (B) can be calculated from the number of ester groups [—C (═O) O—] in (B).

The absolute value of the difference between the ester group concentration based on the weight (A) of the crystalline resin (A) and the ester group concentration based on the weight (B) of the vinyl resin (B) having an ester group is the low temperature fixability. From this viewpoint, it is preferably 45% by weight or less, more preferably 40% by weight or less, and particularly preferably 35% by weight or less.

The SP value of the vinyl resin (B) having an ester group is preferably 9.5 to 11.5 (cal / cm ³ ) ^1/2 from the viewpoint of low-temperature fixability, and more preferably 9.5 to 11 0.0 (cal / cm ³ ) ^1/2 , particularly preferably 10.0 to 11.0 (cal / cm ³ ) ^1/2 .

The absolute value of the difference in SP value between the crystalline resin (A) and the vinyl resin (B) having an ester group is preferably 1.8 (cal / cm ³ ) ^1/2 or less from the viewpoint of low-temperature fixability, More preferably, it is 1.6 or less, Especially preferably, it is 1.4 or less.

The storage elastic modulus G ′ (120) at 120 ° C. of the vinyl resin (B) having an ester group is preferably 1,000 to 1 × 10 ⁶ [Pa · s], more preferably from the viewpoint of low-temperature fixability. Is 3,000 to ⁵ × 10 ⁵ [Pa · s], particularly preferably 5,000 to 1 × 10 ⁵ [Pa · s].

  The vinyl resin (B) having an ester group in the present invention may contain a vinyl resin having two or more ester groups having different Tg or Mw.

  The toner (Z) obtained by the production method of the present invention may contain a resin other than the above crystalline resin (A) and vinyl resin (B) having an ester group. The resin can be contained in (Z) by containing it in advance when obtaining the dispersion liquid (W).

Examples of the resin other than the crystalline resin (A) and the vinyl resin (B) having an ester group include, for example, amorphous polyester, amorphous polyamide, amorphous polyester amide, amorphous polyurethane, amorphous Polyester urethane, hybrid resin in which crystalline resin (A) and vinyl resin (B) having ester group are partially chemically bonded, amorphous polyester and vinyl resin (B) having ester group are partially chemically bonded A hybrid resin or the like may be contained.

As the colorant in the present invention, all of dyes, pigments and the like used as toner colorants can be used. From the viewpoint of durability, black colorants, blue colorants, red colorants and yellow colors are used. It preferably contains at least one selected from the group consisting of colorants.
Examples of the black colorant include carbon black, titanium black, magnetic powder (such as iron oxide zinc and iron oxide nickel).
Examples of blue colorants include copper phthalocyanine pigments and anthraquinone pigments. Specifically, C.I. I. Pigment Blue 2, 3, 6, 15, 15: 1, 15: 2, 15: 3, 15: 4, 16, 17: 1 and 60, and the like.
Examples of the yellow colorant include azo pigments such as monoazo pigments and disazo pigments, and condensed polycyclic pigments. Specifically, C.I. I. Pigment Yellow 3, 12, 13, 14, 15, 17, 62, 65, 73, 74, 83, 93, 97, 120, 138, 155, 180, 181, 185, 186, and the like.
As the red colorant, azo pigments such as monoazo pigments and disazo pigments, and compounds such as condensed polycyclic pigments are used. Specifically, C.I. I. Pigment Red 31, 48, 57: 1, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 144, 146, 149, 150, 163, 170 , 184, 185, 187, 202, 206, 207, 209, 251 and C.I. I. Pigment Violet 19 and the like.

The resin particles (Z ′) in the present invention contain a colorant, a crystalline resin (A), and a vinyl resin (B) having an ester group.
An aqueous medium is mentioned as a dispersion medium which comprises a dispersion liquid (W).
The aqueous medium can be used without limitation as long as it is a liquid containing water as an essential component, and water, an aqueous solution of a solvent, an aqueous solution of a surfactant, an aqueous solution of a synthetic polymer dispersant, and a mixture thereof can be used. .
Examples of the solvent include, among the above organic solvents, esters or ester ether solvents, ether solvents, ketone solvents, alcohol solvents, amide solvents, sulfoxide solvents, heterocyclic compound solvents, and mixed solvents of two or more thereof. It is done. When the solvent is contained, the content of the solvent is preferably 0.1 to 80% by weight based on the weight of the aqueous medium. It is more preferably 1 to 70% by weight, particularly preferably 5 to 30% by weight.

The volume average particle size of the resin particles (Z ′) is preferably 0.050 to 1 μm, more preferably 0.1 to 0.5 μm, and particularly preferably 0.2 to 0.4 μm.
The volume average particle diameter of the resin particles (Z ′) can be measured using a Coulter counter “Multisizer III” (manufactured by Beckman Coulter, Inc.).

Although the method of obtaining a dispersion liquid (W) is not specifically limited, The following [1]-[10] are mentioned.
[1] A method for producing a dispersion (W) by dispersing a colorant, a polyester resin (A), and a vinyl resin (B) having an ester group in an aqueous medium in the presence of an appropriate dispersant if necessary. .
[2] An organic solvent solution of a polyester resin (A) and a vinyl resin (B) having an ester group, and a colorant are dispersed in an aqueous medium in the presence of an appropriate dispersant if necessary, and a dispersion (W ).
[3] An organic solvent solution of a polyester resin (A) and a vinyl resin (B) having an ester group, and a colorant are dispersed in an aqueous medium in the presence of an appropriate dispersant if necessary, and then an organic solvent is used. A method for producing a dispersion liquid (W) by removing water.
[4] An aqueous dispersion in which a colorant is dispersed in an aqueous medium, an aqueous dispersion in which a polyester resin (A) is dispersed in an aqueous medium, and a vinyl resin (B) having an ester group in the aqueous medium A method for preparing a dispersion liquid (W) by preparing aqueous dispersion liquids in which water is dispersed and mixing them. In preparing each aqueous dispersion, an appropriate dispersant can be used if necessary. In the case of a vinyl resin (B) having an ester group, an aqueous dispersion can be prepared by suspension polymerization, emulsion polymerization or the like.
[5] Disperse the colorant, the precursor of the polyester resin (A) and the vinyl resin (B) having an ester group, or an organic solvent solution thereof in an aqueous medium in the presence of an appropriate dispersant if necessary. Then, (A) is produced from the precursor (A) to produce the dispersion liquid (W).
[6] Disperse the colorant, the polyester resin (A) and the precursor of the vinyl resin (B) having an ester group, or an organic solvent solution thereof in an aqueous medium in the presence of a suitable dispersant if necessary. Then, (B) is produced from the precursor of (B) to produce the dispersion liquid (W).
[7] A coloring agent, a precursor of the polyester resin (A) and a precursor of the vinyl resin (B) having an ester group, or an organic solvent solution thereof in an aqueous medium in the presence of a suitable dispersant if necessary. A dispersion liquid (W) is produced by dispersing (A) and (B) from the precursor (A) and the precursor (B), respectively.
[8] A resin containing a colorant, a polyester resin (A) and a vinyl resin (B) having an ester group is pulverized using a mechanical pulverizer such as a mechanical rotary type or a jet type, and then classified. A method of dispersing in an aqueous medium in the presence of a dispersant.
[9] After obtaining particles by spraying a resin solution in which a resin containing a colorant, a polyester resin (A) and a vinyl resin (B) having an ester group is dissolved in an organic solvent, the particles are obtained. Is dispersed in an aqueous medium in the presence of a suitable dispersant.
[10] A resin in which a poor solvent is added to a resin solution obtained by dissolving a resin containing a colorant, a polyester resin (A), and a vinyl resin (B) having an ester group in an organic solvent, or previously dissolved in an organic solvent by heating. A method of precipitating particles by cooling the solution, then removing the organic solvent, and then dispersing in an aqueous medium in the presence of a suitable dispersant.

As the dispersant in the above methods [1] to [10], known surfactants, inorganic dispersants, water-soluble polymers and the like can be used. Moreover, an organic solvent, a plasticizer, etc. can be used together as an auxiliary agent for emulsification or dispersion.

  Examples of the surfactant include an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant. Two or more surfactants may be used in combination.

  Examples of the anionic surfactant include ether carboxylic acids (salts) having an alkyl group having 8 to 24 carbon atoms [(poly) oxyethylene (1 to 100 repeating units) sodium lauryl ether acetate, etc.], 8 to 24 carbon atoms. Ether sulfate ester salt [(poly) oxyethylene (repeating unit number 1 to 100) sodium lauryl sulfate etc.], sulfosuccinic acid ester salt [mono or dialkyl sulfosuccinic acid ester di having 8 to 24 carbon atoms] Or monosodium, (poly) oxyethylene (1 to 100 repeating units) mono or dialkyl sulfosuccinic acid ester di or monosodium], (poly) oxyethylene (1 to 100 repeating units) coconut oil fatty acid monoethanolamide sodium sulfate , A carbon number 8-24 Sulfate having a kill group (sodium dodecylbenzenesulfonate, etc.), phosphate ester salt having an alkyl group having 8 to 24 carbon atoms [sodium lauryl phosphate and (poly) oxyethylene (number of repeating units 1 to 100) lauryl Sodium ether phosphate, etc.], fatty acid salts (sodium laurate, triethanolamine laurate, etc.), acylated amino acid salts (coconut oil fatty acid methyl taurine sodium, coconut oil fatty acid sarcosine sodium, coconut oil fatty acid sarcosine triethanolamine, N- Coconut oil fatty acid acyl-L-glutamic acid triethanolamine, N-coconut oil fatty acid acyl-L-glutamic acid sodium, and lauroylmethyl-β-alanine sodium).

  Examples of the cationic surfactant include quaternary ammonium salt type and amine salt type cationic surfactants. Quaternary ammonium salt type cationic surfactants include tertiary amines and quaternizing agents [alkyl halides (methyl chloride, methyl bromide, ethyl chloride, benzyl chloride, etc.), dimethyl sulfate, dimethyl carbonate, ethylene oxide, etc.] Can be used, for example, lauryltrimethylammonium chloride, didecyldimethylammonium chloride, dioctyldimethylammonium bromide, stearyltrimethylammonium bromide, lauryldimethylbenzylammonium chloride (benzalkonium chloride), cetylpyridinium chloride, Examples include polyoxyethylene trimethyl ammonium chloride and stearamide ethyl diethyl methyl ammonium methosulfate. It is. As amine salt type cationic surfactants, primary to tertiary amines are inorganic acids (hydrochloric acid, nitric acid, sulfuric acid, hydroiodic acid, etc.) or organic acids (acetic acid, formic acid, oxalic acid, lactic acid, gluconic acid, adipic acid. And a compound obtained by neutralization with alkyl phosphoric acid, etc., and primary amine salt type compounds include higher aliphatic amines (such as laurylamine, stearylamine, cetylamine, hardened tallow amine, and rosinamine). Amine) inorganic acid salts or organic acid salts, and higher fatty acid (such as stearic acid and oleic acid) salts of lower amines. Examples of the secondary amine salt type include inorganic acid salts or organic acid salts such as ethylene oxide adducts of aliphatic amines.

  Examples of amphoteric surfactants include carboxybetaine-type amphoteric surfactants [fatty acid amidopropyldimethylaminoacetic acid betaines having 10 to 18 carbon atoms (such as coconut oil fatty acid amidopropyl betaine), alkyl (carbon number 10 to 18) dimethylaminoacetic acid betaines. (Lauryldimethylaminoacetic acid betaine, etc.), imidazolinium-type carboxybetaine (2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, etc.)], sulfobetaine-type amphoteric surfactant [10 to 18 carbon atoms] Fatty acid amidopropylhydroxyethylsulfobetaine (coconut oil fatty acid amidopropyldimethylhydroxyethylsulfobetaine, etc.), dimethylalkyl (10 to 18 carbon atoms) dimethylhydroxyethylsulfobetaine (lauryl hydroxysulfobetaine) Etc.), amino acid type amphoteric surfactants [beta-lauryl amino sodium propionate, etc.] and the like.

Examples of the nonionic surfactant include alkylene oxide addition type nonionic surfactants and polyhydric alcohol type nonionic surfactants.
Examples of the alkylene oxide addition type nonionic surfactant include higher alcohols (8 to 18 carbon atoms) alkylene (2 to 4 carbon atoms, preferably 2) oxide adducts (1 to 1 moles added per active hydrogen). 30), alkyl (carbon number 1-12) phenol ethylene oxide adduct (addition mole number 1-30), higher amine (carbon number 8-22) alkylene (carbon number 2-4, preferably 2) oxide adduct (Addition mole number per active hydrogen 1-40), fatty acid (carbon number 8-18) ethylene oxide adduct (addition mole number 1-60 per active hydrogen), polypropylene glycol (number average molecular weight 200- 4,000) ethylene oxide adduct (number of added moles per active hydrogen 1-50), polyoxyethylene (number of repeating units 3-30) Rualkyl (6 to 20 carbon atoms) allyl ether and sorbitan monolaurate ethylene oxide adduct (1 to 30 addition moles per active hydrogen) and sorbitan monooleate ethylene oxide adduct (addition moles per active hydrogen) Fatty acid (carbon number 8-24) ester ethylene oxide adduct (number of added moles per active hydrogen 1) of polyvalent (2-8 valent or higher) alcohol (2-30 carbon atoms) ~ 30) and the like.
Examples of the polyhydric alcohol type nonionic surfactant include polyvalent (2 to 8 or more) alcohols (2 to 30 carbon atoms) such as glycerol monostearate, glycerol monooleate, sorbitan monolaurate and sorbitan monooleate. ) Fatty acid (carbon number 8-24) ester and fatty acid (carbon number 10-18) alkanolamide such as lauric acid monoethanolamide and lauric acid diethanolamide.

  Inorganic dispersants include tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, hydroxyapatite and other phosphate polyvalent metal salts, carbonates such as calcium carbonate and magnesium carbonate, calcium metasuccinate, sulfuric acid Examples thereof include inorganic salts such as calcium and barium sulfate, and inorganic compounds such as calcium hydroxide, magnesium hydroxide, and aluminum hydroxide.

  Examples of water-soluble polymers include cellulose compounds (methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose and saponified products thereof), gelatin, starch, dextrin, gum arabic, chitin, chitosan, polyvinyl alcohol, Polyvinyl pyrrolidone, polyethylene glycol, polyethyleneimine, polyacrylamide, acrylic acid (salt) polymer (sodium polyacrylate, potassium polyacrylate, ammonium polyacrylate, partially neutralized sodium hydroxide of polyacrylic acid and sodium acrylate -Acrylic acid ester copolymer, etc.), sodium hydroxide (partial) neutralized product of styrene-maleic anhydride copolymer, and Soluble polyurethane (reaction product of polyethylene glycol and polycaprolactone diol with polyisocyanate etc.) and the like.

Plasticizers include phthalate esters (dibutyl phthalate, dioctyl phthalate, butylbenzyl phthalate, diisodecyl phthalate, etc.); aliphatic dibasic acid esters (di-2-ethylhexyl adipate, 2-ethylhexyl sebacate, etc.) ); Trimellitic acid esters (trimellitic acid tri-2-ethylhexyl and trimellitic acid trioctyl); phosphoric acid esters (triethyl phosphate, tri-2-ethylhexyl phosphate, tricresyl phosphate, etc.); fatty acid esters (oleic acid) Butyl, etc.); and mixtures of two or more thereof.

A dispersing machine can be used for dispersion in the above methods [1] to [10].
The disperser is not particularly limited as long as it is generally commercially available as an emulsifier or a disperser. For example, a batch emulsifier {“homogenizer” (manufactured by IKA), “polytron” (manufactured by Kinematica) and “ TK Auto Homo Mixer "[manufactured by Primix Co., Ltd.]}, continuous emulsifier {" Ebara Milder "[manufactured by Ebara Corporation]," TK Filmix "," TK Pipeline Homo Mixer "[Primix ( Co., Ltd.], “Colloid Mill” [manufactured by Shinko Pantech Co., Ltd.], “Slasher”, “Trigonal Wet Fine Crusher” [Suntech Co., Ltd.], “Capitol” (manufactured by Eurotech) and “Fine” Flow Mill "[manufactured by Taiheiyo Kiko Co., Ltd.]}, high-pressure emulsifier {" Microfluidizer "[manufactured by Mizuho Industry Co., Ltd.]," Nanomizer "[SG Njiniaring Co., Ltd.] and "APV Gaurin" (manufactured by Gaurin Co., Ltd.)}, membrane emulsifier {"membrane emulsifier" [manufactured by Chilling Industries Co., Ltd.]}, vibratory emulsifier {"Vibro mixer" Etc.}, an ultrasonic emulsifier {“ultrasonic homogenizer” (manufactured by Branson), etc.}, and the like.

Examples of the method for obtaining the aggregate (Y) of the dispersion (X) in the dispersion (W) include a method of adding an aggregating agent to the dispersion (W).
Flocculants include acids (hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid, etc.), inorganic acid metal salts (sodium chloride, magnesium chloride, calcium chloride, aluminum chloride, aluminum sulfate, calcium sulfate, ammonium sulfate, aluminum nitrate, silver nitrate) , Copper sulfate and sodium carbonate, etc.), fatty acid metal salts (sodium acetate, potassium formate, sodium oxalate, sodium phthalate and potassium salicylate, etc.), aromatic fatty acid metal salts (sodium benzoate, etc.), phenolic metals Examples thereof include salts (such as sodium phenolate) and amine salts (such as metal salts of amino acids, triethanolamine hydrochloride and aniline hydrochloride).
Among these, a metal salt of an inorganic acid and a metal salt of a fatty acid are preferable, and a metal salt of an inorganic acid is more preferable.

The addition amount of the flocculant is preferably 1 to 20% by weight, more preferably 1 to 15% by weight, based on the weight of the resin particles (Z ′).

The heating temperature in the step of obtaining the resin particles (Z ′) by heat fusion of the aggregate (Y) is preferably 30 to 100 ° C., more preferably 40 to 100 ° C.
The heating time is preferably 1 to 12 hours, more preferably 2 to 10 hours.

The toner (Z) obtained by the production method of the present invention may further contain a release agent, a charge control agent and / or a fluidizing agent. They can be contained in (Z) by containing them in advance when the dispersion liquid (W) is obtained.

Release agents include natural waxes (such as beeswax, carnauba wax, and montan wax), petroleum waxes (such as paraffin wax, microcrystalline wax, and petrolatum), and synthetic waxes (polyethylene wax, polypropylene wax, oxidized polyethylene wax, and oxidized polypropylene). Wax, etc.), synthetic ester wax (fatty acid ester synthesized from a C10-30 fatty acid and a C10-30 alcohol), and the like.

The release agent Ta is preferably 40 to 90 ° C., more preferably 45 to 85 ° C., and particularly preferably 50 to 80 ° C. from the viewpoint of low-temperature fixability and gloss.

Kinematic viscosity at 100 ° C. of the releasing agent is preferably from the viewpoint of low-temperature fixing property and gloss is 3~20 ^[mm 2 / s], is more preferably 4~19 ^[mm 2 / s], particularly preferably 5 It is -18 [mm < ² > / s].

As charge control agents, nigrosine compounds, triphenylmethane compounds containing tertiary amines as side chains, quaternary ammonium salts, polyamine resins, imidazole derivatives, quaternary ammonium base-containing polymers, metal-containing azo compounds, copper phthalocyanine compounds , 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.

The charge control agent may be dispersed inside the toner (Z), may cover the (Z) surface, may be dispersed inside (Z) and may cover the (Z) surface. .

Examples of the fluidizing agent include silica, titania, alumina, fatty acid metal salts, silicone resins, and fluororesins, and preferably contain at least two selected from the group consisting of these fluidizing agents.

  The fluidizing agent may be either spherical or irregular, but is preferably spherical from the viewpoint of the fluidity of the toner (Z). The primary particle of the fluidizing agent preferably has a volume average particle diameter of 5 to 300 nm, and two or more kinds having different particle diameters may be used in combination. Specifically, the fluidizing agent 1 having a primary particle volume average particle size of 10 to 100 nm and the fluidizing agent 2 having a primary particle volume average particle size of 70 to 200 nm are preferably used in combination.

The content of each component constituting the toner (Z) obtained by the production method of the present invention is as follows.
The content of the crystalline resin (A) is preferably 5 to 30% by weight, more preferably 6 to 25% by weight, and particularly preferably 7 to 20% by weight based on the weight of (Z).
The content of the vinyl resin (B) having an ester group is preferably 50 to 95% by weight, more preferably 55 to 90% by weight, particularly preferably 60 to 85% by weight, based on the weight of (Z). is there.
The content of the colorant is preferably 0.1 to 60% by weight, more preferably 0.2 to 55% by weight, and particularly preferably 0.5 to 50% by weight, based on the weight of (Z). .
The content of the release agent is preferably 0 to 30% by weight, more preferably 0.5 to 20% by weight, and particularly preferably 1 to 10% by weight based on the weight of (Z).
The content of the charge control agent is preferably 0 to 20% by weight, more preferably 0.1 to 10% by weight, particularly preferably 0.2 to 7.5% by weight, based on the weight of (Z). is there.
The content of the fluidizing agent is preferably 0 to 10% by weight, more preferably 0.2 to 5.0% by weight, particularly preferably 0.3 to 4% by weight, based on the weight of (Z). is there.

  The toner (Z) obtained by the production method of the present invention is coated on the surface with carrier particles [iron powder, glass beads, nickel powder, ferrite, magnetite and resin (acrylic resin, silicone resin, etc.) as necessary. It can be used as a developer for an electrical latent image by mixing with ferrite or the like. Also, instead of carrier particles, it can be rubbed with a charging blade or the like to form an electric latent image. The electric latent image can be obtained by a known heat roll fixing method, heat belt fixing method, flash fixing method, etc. And fixed to a support (paper, polyester film, etc.).

  The toner (Z) obtained by the production method of the present invention preferably satisfies the following [Condition 1] from the viewpoint of heat-resistant storage stability, heat-and-moisture storage resistance and low-temperature fixability.

[Condition 1]
1.1 ≦ (Tg1) / (Tg2) ≦ 3.5
However, (Tg1) represents Tg [° C] detected when the temperature of the differential scanning calorimetry of the toner (Z) is increased by 10 ° C./min from the measurement start temperature of 20 ° C. to the measurement end temperature of 150 ° C. ); When Tg1 is measured by differential scanning calorimetry of toner (Z), then cooled from 150 ° C. to −20 ° C. at 10 ° C./min, and the temperature is increased from −20 ° C. to the measurement end temperature of 150 ° C. at 10 ° C./min. Tg [° C.] detected in.

  Furthermore, in condition 1, (Tg1) / (Tg2) is preferably 1.5 or less, and more preferably 3.0 or less.

In the present invention, Tg can be measured by the following method.
<Measurement method of Tg>
Measurement is performed using a differential scanning calorimeter (DSC) {for example, “DSC210” [manufactured by Seiko Instruments Inc.]}.
Tg is a physical property peculiar to the amorphous part in the resin, and is distinguished from the maximum peak temperature of heat of fusion. Further, in the measurement of the maximum peak temperature (Ta) of the heat of fusion, an extension of the baseline below the maximum peak temperature in the graph of “endothermic heat generation” and “temperature” and the maximum peak from the rising portion of the maximum peak Let Tg be the temperature corresponding to the intersection with the tangent that indicates the maximum slope to the apex.
As a measurement procedure, 4 to 6 mg of a sample is precisely weighed, enclosed in an aluminum pan, and set in a sample holder. The reference uses an empty aluminum pan. As a measurement condition, Tg detected when the temperature is raised by 10 ° C. per minute from the measurement start temperature 20 ° C. to the measurement end temperature 150 ° C. is (Tg 1). Further, after Tg1 measurement, the Tg detected when cooling from 150 ° C. to −20 ° C. at 10 ° C./min and increasing the temperature from −20 ° C. to the measurement end temperature of 150 ° C. at 10 ° C./min is defined as (Tg2). .

The volume average particle diameter of the toner (Z) obtained by the production method of the present invention is preferably 1 to 15 μm, more preferably 2 to 10 μm, and particularly preferably 3 to 8 μm.
The volume average particle size of (Z) can be measured using a Coulter counter “Multisizer III” (manufactured by Beckman Coulter, Inc.).

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to these.

<Production Example 1> [Synthesis of Crystalline Resin (A-1)]
In a reaction vessel equipped with a stirrer, heating / cooling device, thermometer, cooling pipe and nitrogen introduction pipe, 284 parts by weight of ethylene glycol, 650 parts by weight of adipic acid, and 2.5 parts by weight of titanium diisopropoxybistriethanolamate as a polymerization catalyst The temperature was raised to 180 ° C., and the reaction was conducted for 4 hours while distilling off the water generated under the nitrogen stream at the same temperature. Then, the temperature was raised to 220 ° C., and the water produced under the nitrogen stream was distilled off. The reaction was continued for 4 hours. Furthermore, it was made to react until the acid value became 0.5 or less, distilling off water under reduced pressure of 0.007 to 0.026 MPa at the same temperature. Then, it cooled to 180 degreeC, 25 weight part of trimellitic anhydride was put into reaction container, and it was made to react at 180 degreeC for 1 hour, and crystalline resin (A-1) was obtained.

<Production Example 2> [Synthesis of Crystalline Resin (A-2)]
In the same manner as in Production Example 1, except that 284 parts by weight of ethylene glycol and 650 parts by weight of adipic acid were replaced by 254 parts by weight of 1,4-butanediol and 617 parts by weight of dodecanedioic acid, a crystalline resin (A -2) was obtained.

<Production Example 3> [Synthesis of Crystalline Resin (A-3)]
In the same manner as in Production Example 1 except that 284 parts by weight of ethylene glycol and 650 parts by weight of adipic acid were replaced with 408 parts by weight of 1,12-dodecanediol and 434 parts by weight of dodecanedioic acid in Production Example 1, a crystalline resin (A -3) was obtained.

<Production Example 4> [Synthesis of Crystalline Resin (A-4)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling tube and a nitrogen introduction tube, 379 parts by weight of 1,6-hexanediol, 572 parts by weight of sebacic acid, and 2 parts by weight of tetrabutoxy titanate as a polymerization catalyst were added. The temperature is raised to 180 ° C., the reaction is carried out for 4 hours while distilling off the water produced under the nitrogen stream at the same temperature, and then the water produced under the nitrogen stream is distilled off while gradually raising the temperature to 220 ° C. The reaction was conducted for 4 hours, and the reaction was conducted while distilling off water under a reduced pressure of 0.007 to 0.026 MPa. When the acid value became 0.2 [mgKOH / g] or less, the reaction product was taken out, and polyester diol (P- 4) 850 parts by weight were obtained. The hydroxyl value of (P-4) was 51 [mgKOH / g].
(P-4) 850 parts by weight of methyl ethyl ketone was put into a reaction vessel containing 850 parts by weight, and stirred at 60 ° C. for 1 hour to obtain a solution. Next, 53 parts by weight of hexamethylene diisocyanate was added to this solution and reacted at 80 ° C. for 7 hours. Then, 21 parts by weight of trimellitic anhydride was added, heated to 150 ° C. and reacted for 4 hours, and then MEK was distilled. To give a crystalline resin (A-4).

<Comparative Production Example 1> [Synthesis of Amorphous Resin (RA-1)]
In Production Example 1, 284 parts by weight of ethylene glycol and 650 parts by weight of adipic acid were replaced with 452 parts by weight of bisphenol A / PO2 molar adduct, 116 parts by weight of terephthalic acid, and 116 parts by weight of isophthalic acid. Thus, an amorphous resin (RA-1) was obtained. (RA-1) is an amorphous resin because it does not have a clear Ta.

Table 1 shows physical property values of the crystalline resins (A-1) to (A-4) and the amorphous resin (RA-1).

<Production Example 5> [Synthesis of ester resin-containing vinyl resin dispersion (BD-1)]
60 parts by weight of styrene, 28 parts by weight of n-butyl acrylate, 10 parts by weight of methyl methacrylate and 2 parts by weight of acrylic acid were weighed, stirred and homogenized to obtain an oily liquid.
Further, 10.0 parts by weight of tricalcium phosphate was added to 800 parts by weight of ion-exchanged water to adjust the aqueous medium, and the temperature was adjusted to 70 ° C. To the oily liquid, 4.0 parts by weight of t-butyl peroxypivalate as a polymerization initiator is added, and this is put into an aqueous medium, and stirred at 10,000 rpm for 5 minutes with a TK auto homomixer. Dispersed in the medium. Thereafter, the stirrer was changed to a propeller stirring blade, and polymerization was carried out for 8.0 hours while maintaining 70 ° C. while stirring at 200 rpm.
As a result, a vinyl resin dispersion (BD-1) having an ester group with a volume average particle size of 200 nm was obtained. The solid content concentration of this dispersion was 50% by weight.

<Production Example 6> [Synthesis of ester resin-containing vinyl resin dispersion (BD-2)]
In Production Example 5, styrene 60 parts by weight, n-butyl methacrylate 28 parts by weight, methyl methacrylate 10 parts by weight, acrylic acid 2 parts by weight, n-butyl acrylate 28 parts by weight, methyl methacrylate 70 parts by weight, acrylic acid A vinyl resin dispersion (BD-2) having an ester group with a volume average particle size of 200 nm was obtained in the same manner as in Production Example 5 except that the amount was changed to 2 parts by weight. The solid content concentration of this dispersion was 50% by weight.

<Production Example 7> [Synthesis of ester resin-containing vinyl resin dispersion (BD-3)]
In Production Example 5, styrene 60 parts by weight, n-butyl acrylate 28 parts by weight, methyl methacrylate 10 parts by weight, acrylic acid 2 parts by weight, n-butyl acrylate 28 parts by weight, methyl acrylate 70 parts by weight, acrylic acid 2 parts by weight A vinyl resin dispersion (BD-3) having an ester group with a volume average particle diameter of 200 nm was obtained in the same manner as in Production Example 5 except that the parts were replaced with parts. The solid content concentration of this dispersion was 50% by weight.

<Production Example 8> [Synthesis of ester resin-containing vinyl resin dispersion (BD-4)]
In Production Example 5, styrene 60 parts by weight, n-butyl acrylate 28 parts by weight, methyl methacrylate 10 parts by weight, acrylic acid 2 parts by weight, styrene 30 parts by weight, n-butyl acrylate 27 parts by weight, methyl methacrylate 40 parts by weight A vinyl resin dispersion (BD-4) having an ester group with a volume average particle size of 150 nm was obtained in the same manner as in Production Example 5 except that the amount was replaced with 3 parts by weight of acrylic acid. The solid content concentration of this dispersion was 50% by weight.

<Production Example 9> [Synthesis of vinyl resin dispersion having ester group (BD-5)]
In Production Example 5, 60 parts by weight of styrene, 28 parts by weight of n-butyl acrylate, 10 parts by weight of methyl methacrylate, 2 parts by weight of acrylic acid, and 4.0 parts by weight of t-butyl peroxypivalate were 28 parts by weight of n-butyl acrylate. Parts in the same manner as in Production Example 5 except that the components were replaced with 4 parts by weight of methyl methacrylate, 70 parts by weight of methyl methacrylate, 2 parts by weight of acrylic acid, and 2,2 parts of 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane. A vinyl resin dispersion (BD-5) having an ester group with a volume average particle size of 200 nm was obtained. The solid content concentration of this dispersion was 50% by weight.

<Comparative Production Example 2> [Synthesis of copolymer dispersion (RBD-1)]
In Production Example 5, Production Example 5 except that 60 parts by weight of styrene, 28 parts by weight of n-butyl acrylate, 10 parts by weight of methyl methacrylate, and 2 parts by weight of acrylic acid were replaced with 98 parts by weight of styrene and 2 parts by weight of acrylic acid. Similarly, a copolymer dispersion (RBD-1) was obtained.

<Comparative Production Example 3> [Synthesis of copolymer dispersion (RBD-2)]
In Production Example 9, n-butyl acrylate 28 parts by weight, methyl methacrylate 70 parts by weight, acrylic acid 2 parts by weight was replaced with styrene 98 parts by weight, acrylic acid 2 parts by weight in the same manner as in Production Example 5, A copolymer dispersion (RBD-2) was obtained.

Dispersions (BD-1) to (BD-5), (RBD-1), and (RBD-2) were dried to obtain samples for analysis. Table 2 shows physical property values of vinyl resins (LB-1) to (LB-4), (HB-1), (RLB-1), and (RHB-1) having ester groups of the obtained samples.

<Production Example 10> [Production of crystalline resin dispersion (AD-1)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling pipe, and a thermometer, 15 parts by weight of the resin (A-1) produced in Production Example 1 and 20 parts by weight of ion-exchanged water are added, and the mixture is stirred at 90 ° C. The temperature is raised and stirred for 30 minutes at the same temperature, then cooled to 10 ° C. over 1 hour to crystallize the crystalline resin into fine particles, and then wet pulverized with Ultraviscomil (manufactured by IMEX) to disperse the crystalline resin. A liquid (AD-1) was obtained. The volume average particle diameter of (AD-1) was 0.5 μm, and the solid content concentration was 50% by weight.

<Production Example 11> [Production of crystalline resin dispersion (AD-2)]
A crystalline resin dispersion (AD-2) was obtained in the same manner as in Production Example 10 except that 15 parts by weight of the resin (A-1) was replaced with the resin (A-2) in Production Example 10. The volume average particle diameter of (AD-2) was 0.5 μm, and the solid content concentration was 50% by weight.

<Production Example 12> [Production of crystalline resin dispersion (AD-3)]
A crystalline resin dispersion (AD-3) was obtained in the same manner as in Production Example 10 except that 15 parts by weight of the resin (A-1) in Production Example 10 was replaced with the resin (A-3). The volume average particle diameter of (AD-3) was 0.5 μm, and the solid content concentration was 50% by weight.

<Production Example 13> [Production of release agent dispersion 1]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling tube and a thermometer, paraffin wax “HNP-9” [Maximum melting heat peak temperature: 73 ° C., manufactured by Nippon Seiki Co., Ltd.] 10 parts by weight, dodecylbenzene 0.5 parts by weight of sodium sulfonate and 15 parts by weight of ion-exchanged water are added, the temperature is raised to 78 ° C. with stirring, the mixture is stirred at the same temperature for 30 minutes, and then cooled to 30 ° C. over 1 hour to form paraffin wax. Crystallized into a shape and wet pulverized with Ultra Visco Mill (manufactured by Imex) to obtain a release agent dispersion 1. The obtained release agent dispersion 1 had a volume average particle diameter of 0.25 μm and a solid content concentration of 50% by weight.

<Production Example 14> [Production of release agent dispersion liquid 2]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling pipe and a thermometer, 10 parts by weight of carnauba wax [maximum heat of fusion peak temperature: 81 ° C.], 0.5 parts by weight of sodium dodecylbenzenesulfonate, 15 ion-exchanged water Add parts by weight, raise the temperature to 90 ° C. with stirring, stir at the same temperature for 30 minutes, cool to 30 ° C. over 1 hour to crystallize carnauba wax into fine particles, and wet pulverize with Ultra Visco Mill As a result, a release agent dispersion 2 was obtained. The resulting release agent dispersion 2 had a volume average particle size of 0.15 μm and a solid content concentration of 50% by weight.

<Production Example 15> [Production of black colorant dispersion]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling pipe and a thermometer, 10 parts by weight of carbon black “MA100” [manufactured by Mitsubishi Chemical Corporation], 0.5 parts by weight of sodium dodecylbenzenesulfonate, ion-exchanged water 40 parts by weight was added, the temperature was raised to 30 ° C. with stirring, the mixture was stirred at the same temperature for 30 minutes, and then wet pulverized with an ultra visco mill to obtain a black colorant dispersion. The resulting black colorant dispersion had a volume average particle size of 0.05 μm and a solid content concentration of 20% by weight.

<Production Example 16> [Production of blue colorant dispersion]
A copper phthalocyanine pigment C.I. I. Pigment Blue 15: 3 “Cyanine Blue 4920” (manufactured by Dainichi Seika Kogyo Co., Ltd.), 10 parts by weight, 0.5 part by weight of sodium dodecylbenzenesulfonate, and 40 parts by weight of ion-exchanged water are added and the temperature is raised to 30 ° C. with stirring The mixture was stirred at the same temperature for 30 minutes, and then wet pulverized with an ultra visco mill to obtain a blue colorant dispersion. The resulting blue colorant dispersion had a volume average particle size of 0.05 μm and a solid content concentration of 20% by weight.

<Examples 1 to 10, Comparative Examples 1 to 4> [Production of Toner (Z)]
A vinyl resin dispersion having an ester group, a crystalline resin dispersion, a release agent dispersion, and a colorant dispersion are placed in a reaction vessel equipped with a stirrer, a heating / cooling device, a temperature sensor, a cooling pipe, and a nitrogen introduction device. The solid content was charged as shown in Table 3, 1,000 parts by weight of ion-exchanged water was charged, the liquid temperature was adjusted to 30 ° C., and then the pH was adjusted to 10 by adding a 25% by weight sodium hydroxide solution. .

Next, an aqueous solution in which 54.3 parts by weight of magnesium chloride hexahydrate is dissolved in 54.3 parts by weight of ion-exchanged water is added, and then the temperature of the system is raised to 60 ° C. The colorant particles, the release agent particles, and the crystalline resin particles were aggregated and fused. After starting, using a particle size distribution measuring device (Coulter Multisizer 3 manufactured by Beckman Coulter, Inc.), sampling is performed as appropriate to confirm that the particle size is 5 μm, and the reaction is stopped by cooling to 30 ° C. A dispersion was obtained. Subsequently, it was washed and separated by filtration, and dried at 40 ° C. for 18 hours to make the volatile content 0.5% by weight or less. Toners (Z-1) to (Z-10) of the present invention having a volume average particle diameter of 5 μm are obtained by uniformly mixing 99 parts by weight of the obtained toner particles and 1 part by weight of colloidal silica (Aerosil R972 manufactured by Nippon Aerosil). Comparative toners (RZ-1) to (RZ-4) were obtained.

For toners (Z-1) to (Z-10) and (RZ-1) to (RZ-4), the styrene monomer content, the monomer content, and the VOC content were measured by the above methods. The low-temperature fixability, gloss, heat-resistant storage stability, wet heat-resistant storage stability, and durability were evaluated, and the results are shown in Table 3.

[1] Low-temperature fixability The toners (Z-1) to (Z-10) and (RZ-1) to (RZ-4) are uniformly placed on the paper surface so as to be 0.6 mg / cm ² (at this time, the powder The method of placing the body on the paper surface uses a printer from which the thermal fixing machine is removed, and other methods may be used as long as the powder can be placed uniformly at the above-mentioned weight density. When this paper was passed through a pressure roller under conditions of a fixing speed (heating roller peripheral speed) of 213 mm / sec and a fixing pressure (pressure roller pressure) of 1 MPa, the temperature at which cold offset occurred was measured. The lower the temperature at which cold offset occurs, the better the low-temperature fixability.

[2] Glossiness Fix an image fixed at 140 ° C. using a gloss meter (VG-1D) (manufactured by Nippon Denshoku Co., Ltd.), adjust the light projection angle and the light reception angle to 60 °, and switch between S and S / 10. In accordance with S, 0 adjustment and a standard plate were used, and after setting the standard, the image was placed on a sample stage, and gloss was measured.
A higher gloss value means higher gloss.

[3] Heat resistant storage stable toners (Z-1) to (Z-10) and (RZ-1) to (RZ-4) are allowed to stand in an atmosphere of 50 ° C. for 1 day, and the following criteria are determined according to the degree of blocking. The heat-resistant storage stability was evaluated.
[Evaluation criteria]
○: Blocking does not occur Δ: Blocking occurs, but disperses easily when force is applied.
X: Blocking occurs and does not disperse even when force is applied.

[4] Humidity and heat storage stability Toners (Z-1) to (Z-10) and (RZ-1) to (RZ-4) are allowed to stand for 20 hours in an atmosphere of 40 ° C. and a relative humidity of 80%. Wet heat and heat storage stability was evaluated according to the following criteria depending on the degree of blocking.
[Evaluation criteria]
○: Blocking does not occur.
Δ: Blocking occurs but disperses easily when force is applied.
X: Blocking occurs and does not disperse even when force is applied.

[5] Durability Commercially available monochrome copying machines [AR5030, manufactured by Sharp Corporation] using toners (Z-1) to (Z-10) and (RZ-1) to (RZ-4) as two-component developers. Using this, continuous copying was performed, and durability was evaluated according to the following criteria.
[Evaluation criteria]
◎ No change in image quality and no fogging after 10,000 copies.
○ Fogging occurs after 10,000 copies.
Δ: Fog is generated after copying 6,000 sheets.
X: Fog occurs after 2,000 copies.

  The toner (Z) obtained by the production method of the present invention can achieve both heat-resistant storage stability, heat-and-moisture storage resistance and low-temperature fixability, and is excellent in toner durability and gloss. It is useful as a toner and electrostatic printing toner.

Claims (18)

A method for producing a toner (Z) comprising a colorant, a crystalline resin (A), and a vinyl resin (B) having an ester group, wherein the colorant, the crystalline resin (A) and the vinyl resin (B) A toner comprising a step of obtaining resin particles (Z ′) by heating and coalescing the aggregate (Y) obtained by aggregating the dispersion (X) in the dispersion (W) containing Z) production method.   The method for producing a toner according to claim 1, wherein the ester group concentration of the vinyl resin (B) having an ester group is 5 to 60% by weight based on the weight of (B).   The toner production according to claim 1 or 2, wherein the crystalline resin (A) is a crystalline resin having at least one functional group selected from the group consisting of an ester group, a urethane group, a urea group, and an amide group. Method. The method for producing a toner according to claim 3, wherein the crystalline resin (A) is a crystalline resin having an ester group.   Difference between ester group concentration (wt%) based on weight of crystalline resin (A) (A) and ester group concentration (wt%) based on the weight of (B) of vinyl resin (B) having an ester group The method for producing a toner according to claim 4, wherein an absolute value of the toner is 45% by weight or less. The absolute value of the difference in solubility parameter between the crystalline resin (A) and the vinyl resin (B) having an ester group is 1.8 (cal / cm ³ ) ^1/2 or less. Toner production method. The method for producing a toner according to claim 1, wherein the toner satisfies condition 1.
[Condition 1]
1.1 ≦ (Tg1) / (Tg2) ≦ 3.5
In the relational expression, (Tg1) represents the glass transition temperature [° C.] detected when the temperature is increased by 10 ° C. per minute from the measurement start temperature 20 ° C. to the measurement end temperature 150 ° C. in the differential scanning calorimetry of the toner.
(Tg2) is Tg1 measured by differential scanning calorimetry of the toner, cooled at 10 ° C./min from 150 ° C. to −20 ° C., and heated at 10 ° C./min from −20 ° C. to the measurement end temperature of 150 ° C. Represents the detected glass transition temperature [° C.].   In the molecular weight distribution obtained by gel permeation chromatography of the vinyl resin (B) having an ester group, at least one peak is present in each of a region having a molecular weight of 3,000 to 30,000 and a region having a molecular weight of 100,000 to 500,000. A method for producing a toner according to any one of claims 1 to 7.   The vinyl resin (B) having an ester group is a vinyl resin having an ester group having a (meth) acrylic acid ester having an alkyl group having 1 to 50 carbon atoms as a structural unit. Toner production method.   The vinyl resin (B) having an ester group is a vinyl resin having an ester group having a structural unit of an aromatic hydrocarbon having a polymerizable double bond and / or an unsaturated monocarboxylic acid having 3 to 15 carbon atoms. The method for producing a toner according to any one of 1 to 9. 11. The toner production according to claim 1, wherein the storage elastic modulus G ′ (120) at 120 ° C. of the vinyl resin (B) having an ester group is 1000 to 1 × 10 ⁶ [Pa · s]. Method.   The method for producing a toner according to claim 1, wherein the maximum temperature (Ta) of the endothermic peak of the crystalline resin (A) is 50 to 100 ° C.   The method for producing a toner according to claim 1, wherein the crystalline resin (A) has a weight average molecular weight of 3,000 to 50,000. The method for producing a toner according to claim 1, wherein the crystalline resin (A) satisfies the following conditions 2 and 3.
[Condition 2]
G ′ (Ta + 10) ≦ 1,000 [Pa · s]
[Condition 3]
1 × 10 ⁶ ≦ G ′ (Ta−10) ≦ 1 × 10 ⁹ [Pa · s]
In the relational expression, G ′ (Ta + 10) represents the storage elastic modulus [Pa · s] of (A) at (Ta + 10) [° C.], and G ′ (Ta−10) represents (Ta−10) [° C.] This represents the storage elastic modulus [Pa · s] of A). The method for producing a toner according to claim 1, wherein the crystalline resin (A) satisfies the condition 4.
[Condition 4]
3 ≦ Log {G ′ (Ta−10)} − Log {G ′ (Ta + 10)} ≦ 8
In the relational expression, G ′ (Ta-10) is the storage elastic modulus [Pa · s] of (A) at (Ta-10) [° C.], and G ′ (Ta + 10) is (A +) at (Ta + 10) [° C.]. ) Storage elastic modulus [Pa · s].   The method for producing a toner according to claim 1, wherein the content of the crystalline resin (A) is 5 to 30% by weight based on the weight of the toner.   The method for producing a toner according to claim 1, wherein the colorant is a colorant containing at least one selected from the group consisting of a black colorant, a blue colorant, a red colorant, and a yellow colorant. . A toner obtained by the production method according to claim 1.