JP2015152793A - toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an inexpensive toner that can achieve a heat-resistant storage property, moist and heat-resistant storage property, and low-temperature fixability, and has excellent toner durability and glossiness.SOLUTION: There is provided a toner that contains a colorant and a binder resin, where the binder resin contains a crystalline resin (A) and a vinyl resin (B) having an ester group.

Description

  The present invention relates to 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 for low-temperature fixability and heat-resistant storage stability, it is insufficient in heat-and-moisture storage stability, and the durability of the toner is reduced, limiting the design of copiers and printers. There is. Furthermore, there is a problem that the cost as a toner is high.
In order to solve these problems, a technique has been proposed in which a crystalline polyester resin is contained in a styrene-acrylic resin that is relatively cheaper than polyester (Patent Document 2). By using a styrene-acrylic resin, the durability of the toner is improved, and the results of good heat and heat storage resistance are obtained. 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 JP 2003-302791 A

  SUMMARY OF THE INVENTION An object of the present invention is to provide an inexpensive toner that can achieve both heat-resistant storage stability, heat-and-moisture storage stability 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 toner having both heat-resistant storage stability, heat-and-moisture storage resistance and low-temperature fixability. That is, the present invention is a toner containing a colorant and a binder resin, wherein the binder resin contains a crystalline resin (A) and a vinyl resin (B) having an ester group.

  The toner of the present invention has both heat-resistant storage stability, heat-and-moisture storage resistance and low-temperature fixability, is excellent in toner durability and gloss, and is inexpensive.

  The toner of the present invention contains a colorant and a binder resin, and the binder resin contains a crystalline resin (A) and a vinyl resin (B) having an ester group.

In the present invention, the crystalline resin means a resin having an endothermic peak temperature of melting heat (hereinafter abbreviated as Ta) having a clear endothermic peak in differential scanning calorimetry (DSC). Ta can be measured by the following method.
<Ta measurement method>
It is measured using a differential scanning calorimeter {for example, “DSC210” [manufactured by Seiko Instruments Inc.]}.
As a pretreatment, a sample to be measured for Ta is melted at 150 ° C., then cooled at a rate of 1.0 ° C./min from 150 ° C. to 70 ° C., and then 0.5 ° C./70° C. to 10 ° C. Lower the temperature at the rate of minutes. Here, DSC is used to measure the endothermic change by increasing the temperature at a rate of temperature increase of 20 ° C./min, drawing a graph of “endothermic amount” and “temperature”, and the endothermic peak temperature observed at this time Is Ta ′. When there are a plurality of peaks, the peak temperature having the largest endothermic amount is defined as Ta ′. Finally, the sample is stored at (Ta′−15) ° C. for 6 hours, and then stored at (Ta′−10) ° C. for 6 hours.
Next, the sample was cooled to 0 ° C. by DSC at a rate of temperature decrease of 10 ° C./min, and then the temperature was increased at a rate of temperature increase of 20 ° C./min to measure the endothermic change. The maximum temperature 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.

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). , Decanediol, dodecanediol, tetradecanediol, neopentyl glycol and 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 and polytetramethylene ether glycol); alicyclic diol having 6 to 24 carbon atoms (for example, 1,4-cyclohexanedi) (Tanol and hydrogenated bisphenol A, etc.); alkylene oxide (hereinafter abbreviated as AO) adduct (addition mole number 2 to 100) of Mn = 100 to 10,000 (for example, 1,4-cyclohexanedi) Ethylene oxide of methanol (hereinafter abbreviated as EO) 10 mol adduct, etc.]; Bisphenols having 15 to 30 carbon atoms (bisphenol A, bisphenol F, bisphenol S, etc.) or polyphenols having 12 to 24 carbon atoms (for example, catechol, hydroquinone) ASO [EO, propylene oxide (hereinafter abbreviated as PO), butylene oxide (hereinafter abbreviated as BO), etc.] adducts (addition mole number 2 to 100) (for example, bisphenol A · EO 2 to 4 mole addition) And bisphenol A · PO 2-4 mol Weight average molecular weight (hereinafter abbreviated as Mw) = 100-5,000 polylactone diol (for example, poly-ε-caprolactone diol, etc.); Mw = 1,000-20,000 polybutadiene diol, etc. Can be mentioned.
Of these, an AO adduct of alkylene glycol and bisphenols is preferred, and an AO adduct of bisphenols and a mixture of an AO adduct of bisphenols and alkylene glycol are more preferred.

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, alkene dicarboxylic acids and aromatic dicarboxylic acids are preferred, and aromatic dicarboxylic acids are more preferred.

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

  As the crystalline polyurethane resin (A2), the diol (1) and / or the diamine (3) and the diisocyanate (4) as structural units (A2-1), and the crystalline polyester resin (A1), Examples thereof include those having the diol (1) and / or diamine (3) and diisocyanate (4) as structural units (A2-2).

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.

  The aromatic diamine having an alkyl group (alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, n- or isopropyl group and butyl group) includes 2,4- or 2,6-tolylenediamine, crude Tolylenediamine, diethyltolylenediamine, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 4,4′-bis (o-toluidine), dianisidine, diaminoditolylsulfone, 1,3-dimethyl-2 , 4-diaminobenzene, 1,3-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, '-Diaminodiphenylmethane, 3,3', 5,5'-tetrabutyl-4,4'-diaminodiphenylmethane, 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'-diaminodiphenyl sulfone and mixtures thereof Can be mentioned.

  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 modified product of these diisocyanates (urethane group, Carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group and oxazolidone group-containing modified product) and mixtures of two or more thereof.

  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.
Cycloaliphatic 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 the 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 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.

O— (R ¹ O) _m SO ₃ H
｜
_{CH 2 = CHCH 2 OCH 2 CHCH} 2 O-Ar-R 2 (1)



CH = CH-CH ₃
｜
R ³ —Ar—O— (R ¹ O) _n SO ₃ H (2)

CH ₂ COOR ⁴
｜
HOSO ₂ CHCOOCH ₂ CH (OH) CH ₂ OCH ₂ CH═CH ₂ (3)

In the formula, R ¹ is an alkylene group having 2 to 4 carbon atoms, and when there are a plurality of R ¹ O, one type or two or more types may be used, and when two or more types are used in combination, the bonding type 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 is substituted with a fluorine atom. An alkyl group having 1 to 15 carbon atoms may be 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-ethoxyacrylate, alkyl (meth) acrylate having an alkyl group 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) a Relate, etc.], dialkyl fumarate (two alkyl groups are linear, 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) 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 ether 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 By condensation reaction of glycidyl ether of cresol novolak resin, glycidyl ether of limonene phenol novolak resin, diglycidyl ether obtained from the reaction of 2 mol of bisphenol A and 3 mol of epichlorohydrin, phenol and glyoxal, glutaraldehyde or formaldehyde Examples thereof include polyglycidyl ethers of polyphenols obtained and polyglycidyl ethers of polyphenols obtained by 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.

  The acid value of the crystalline resin (A) is preferably 30 KOH mg / g or less, more preferably 25 mg / g, particularly preferably 20 mg / g or less, from the viewpoints of heat and water resistance.

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

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

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, and further satisfies [Condition 2-1] and [Condition 3-1] simultaneously. preferable.
[Condition 2]
G ′ (Ta + 10) ≦ 1,000 [Pa · s]
[Condition 3]
1 × 10 ⁶ ≦ G ′ (Ta−10) ≦ 1 × 10 ⁹ [Pa · s]
[Condition 2-1]
G ′ (Ta + 10) ≦ 800 [Pa · s]
[Condition 3-1]
1 × 10 ⁶ ≦ G ′ (Ta−10) ≦ 1 × 10 ⁸ [Pa · s]
{G ′ (Ta + 10): (A) storage elastic modulus [Pa · s] at (Ta + 10) [° C.], G ′ (Ta-10): (Ta-10) storage elastic modulus at (° C)] Rate [Pa · s]}

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] and more preferably satisfies [Condition 4-1] from the viewpoint of low-temperature fixability and gloss.
[Condition 4]
3 ≦ Log (G ′ (Ta−10)) − Log (G ′ (Ta + 10)) ≦ 8
[Condition 4-1]
3 ≦ Log (G ′ (Ta−10)) − Log (G ′ (Ta + 10)) ≦ 7

  The crystalline resin (A) satisfying [Condition 2], [Condition 2-1], [Condition 3], [Condition 3-1], [Condition 4] and [Condition 4-1] It can be obtained by adjusting the SP value of the crystalline component, adjusting the weight average molecular weight, or the like. For example, in the molecular weight distribution obtained by gel permeation chromatography, when the ratio of the crystalline part having a peak in the low molecular weight region is increased, the value of G ′ (Ta + 10) decreases. Further, by reducing the SP value of (A), the value of G ′ (Ta + 10) becomes smaller.

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.
Of the “(13-1) ester having 4 to 16 carbon atoms having a polymerizable double bond” constituting (B), a (meth) acrylic acid ester is preferred from the viewpoint of low-temperature fixability.

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 monomer arbitrarily selected from the exemplified (5) to (13) may be used as a constituent monomer.
Among these, from the viewpoint of compatibility with the crystalline resin (A), “(6) monomer having carboxyl group and polymerizable double bond”, “(5-2) polymerizable double bond” are preferable. “Aromatic hydrocarbon having a bond” and a combination thereof, and more preferable are an unsaturated monocarboxylic acid having 3 to 15 carbon atoms, styrene, a hydrocarbyl substitution product of styrene, and a combination thereof.
(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 2,000,000, more preferably from 3,500, from the viewpoints of low-temperature fixability, heat-resistant storage stability, wet heat-resistant storage stability and durability. 1.6 million, particularly preferably 4,000 to 1,200,000.

The vinyl resin (B) having an ester group in the present invention has at least one peak in a molecular weight distribution obtained by gel permeation chromatography only in a region having a molecular weight of 3,000 to 60,000 from the viewpoint of low-temperature fixability of the toner. You may have.
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 viewpoint of achieving 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 2,000,000.
More preferred are those having at least one peak in the region of 3,500 to 40,000 and in the region of 120,000 to 1.6 million, and particularly preferred are the region of 4,000 to 20,000. , Each having at least one peak in the region of 140,000 to 1,200,000.

The resin constituting the vinyl resin (B) having an ester group is a resin (LB) having at least one peak in a molecular weight region of 3,000-60,000 in the molecular weight distribution obtained by gel permeation chromatography. Further, it may be a resin (HB) mixture having at least one peak in a molecular weight range of 100,000 to 2,000,000.
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 20,000, from the viewpoint of low-temperature fixability of the toner. is there.

  The Mw of (HB) is preferably 100,000 to 2,000,000, more preferably 120,000 to 1,600,000, particularly preferably 140,000 to 140,000 from the viewpoints of heat resistant storage stability, wet heat storage resistance and durability improvement of the toner. 1.2 million.

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

  The glass transition temperature (Tg) of the vinyl resin (B) having an ester group is preferably 40 to 110 ° C., more preferably 40 to 100 ° C., and particularly preferably 40 to 90 ° C. from the viewpoint of low-temperature fixability of the toner. is there.

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 inorganic acid salt dispersing agents (calcium carbonate, calcium phosphate, etc.), organic dispersing agents (polyvinyl alcohol, methylcellulose, etc.), etc.

The monomer content in the toner is preferably 5,000 ppm or less, more preferably 3000 ppm or less, particularly preferably 1000 ppm or less, based on the weight of the toner, from the viewpoints of heat-resistant storage stability, wet heat storage resistance and durability. It is.
The monomer content in the toner can be measured by gas chromatography.

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

The monomer content in the toner varies depending on the type of monomer used. For example, when it is desired to keep the residual rate of the vinyl monomer low, methyl methacrylate or butyl methacrylate can be used from the viewpoint of the reactivity of the vinyl monomer.
Further, in the aging step after the polymerization reaction of (B), the monomer temperature in the toner is suppressed by polymerizing the residual monomer in the reaction system by setting the process temperature to a temperature 10 ° C. higher than the reaction process. Can do.

The solvent content in the toner is preferably 5,000 ppm or less, more preferably 3,000 ppm or less, and particularly preferably 1 based on the weight of the toner, from the viewpoints of heat-resistant storage, wet heat-resistant storage and durability. 1,000 ppm or less.
The solvent content in the toner can be measured by gas chromatography.

An example of the measurement conditions for measuring the solvent content in the toner by gas chromatography is shown below.
Model: “GC2010” [manufactured by Shimadzu Corporation]
Column: “DB-5” (5% by weight phenylmethylpolysiloxane, inner diameter 0.25 mm,
30m long] [Shimadzu Corporation]
Eluent: Dimethylformamide 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 binder resin in the present invention may contain two or more crystalline resins (A) having different Ta.

  The binder resin in the present invention may contain a vinyl resin having two or more ester groups having different Tg or Mw.

  The binder resin in the present invention may contain a resin other than the above crystalline resin (A) and vinyl resin (B) having an ester group.

  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.

  The content of the crystalline resin (A) in the binder resin in the present invention is preferably 5 to 30 from the viewpoint of compatibility between low-temperature fixability, heat-resistant storage stability and moisture-heat storage resistance based on the weight of the binder resin. % By weight, more preferably 5-25% by weight, particularly preferably 5-20% by weight.

  In the present invention, the content of the vinyl resin (B) having an ester group in the binder resin is based on the weight of the binder resin from the viewpoint of compatibility between low-temperature low-fixability, heat-resistant storage stability and moisture-heat storage stability. Preferably it is 70 to 95 weight%, More preferably, it is 75 to 95 weight%, Most preferably, it is 80 to 95 weight%.

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 toner of the present invention can contain a release agent, a charge control agent, a fluidizing agent, and the like in addition to the colorant and the binder resin.

  The toner of the present invention can further contain a release agent, a charge control agent and / or a fluidizing agent.

  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, may coat the toner surface, or may be dispersed inside the toner and coat the toner 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 toner fluidity. 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 of the present invention is as follows.
The content of the toner binder of the present invention is preferably 30 to 97% by weight, more preferably 40 to 95% by weight, and particularly preferably 45 to 92% by weight based on the weight of the toner.
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 the toner.
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 the toner.
The content of the charge control agent is preferably 0 to 20% by weight, more preferably 0.1 to 10% by weight, and particularly preferably 0.2 to 7.5% by weight based on the weight of the toner.
The content of the fluidizing agent is preferably 0 to 10% by weight, more preferably 0.2 to 5.0% by weight, and particularly preferably 0.3 to 4% by weight based on the weight of the toner.

  The toner of the present invention may be mixed with carrier particles [iron powder, glass beads, nickel powder, ferrite, magnetite, and ferrite (surface coated with acrylic resin, silicone resin, etc.), etc.] as necessary. It can be used as a developer for a target latent image. 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 of the present invention preferably satisfies the following [Condition 1], and satisfies [Condition 1-1], from the viewpoint of heat-resistant storage stability, wet heat storage resistance and low-temperature fixability. Further preferred.
[Condition 1]
1.1 ≦ (Tg1) / (Tg2) ≦ 3.5
[Condition 1-1]
1.5 ≦ (Tg1) / (Tg2) ≦ 3.0
(Tg1); Glass transition temperature [° C.] detected when the temperature is increased by 10 ° C. per minute from the measurement start temperature 20 ° C. to the temperature end 150 ° C. in the differential scanning calorimetry of the toner.
(Tg2): After Tg1 measurement by differential scanning calorimetry of toner, when cooled from 10 ° C./min from 150 ° C. to −20 ° C., and when the temperature was increased from −20 ° C. to 150 ° C. at 10 ° C./min. Detected glass transition temperature [℃]

In the present invention, the glass transition temperature (Tg) can be measured by the following method.
<Glass transition temperature (Tg)>
Measurement is performed using a differential scanning calorimeter (DSC) {for example, “DSC210” [manufactured by Seiko Instruments Inc.]}.
The glass transition temperature is a physical property peculiar to the amorphous part in the resin, and is distinguished from the maximum peak temperature of the 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 The temperature corresponding to the intersection point with the tangent indicating the maximum inclination to the top of the glass transition temperature is defined as the glass transition temperature.
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 the measurement conditions, the glass transition temperature detected when the temperature is raised by 10 ° C. per minute from the measurement start temperature of 20 ° C. to the measurement end temperature of 150 ° C. is defined as (Tg1). Furthermore, after Tg1 measurement, the glass transition temperature detected when cooling from 150 ° C to -20 ° C at 10 ° C per minute and raising the temperature from -20 ° C to the measurement end temperature of 150 ° C at 10 ° C per minute (Tg2) And

The volume average particle size of the toner 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 diameter of the toner can be measured using a Coulter counter “Multisizer III” (manufactured by Beckman Coulter, Inc.).

The method for producing the toner of the present invention is not particularly limited, and may be obtained by a known kneading and pulverizing method, emulsion phase inversion method, polymerization method or the like.
For example, when a toner is obtained by a kneading and pulverizing method, the components constituting the toner excluding the fluidizing agent are dry blended, and then melt-kneaded, then coarsely pulverized, and finally atomized using a jet mill pulverizer or the like. Further, by further classifying, fine particles having a volume average particle diameter of preferably 1 to 15 μm can be obtained and then mixed with a fluidizing agent. When the toner is obtained by the emulsion phase inversion method, the components constituting the toner excluding the fluidizing agent are dissolved or dispersed in an organic solvent, and then emulsified by adding water, etc., and then separated and classified. . Further, it may be produced by a method using organic fine particles described in JP-A No. 2002-284881 or a method of dispersing in carbon dioxide in a supercritical state described in JP-A No. 2007-277511.

  As a method of controlling the particle size of the toner, in the kneading and pulverizing method, the particle size can be controlled by a general method such as reducing the particle size by increasing the air volume of a jet mill or the like. In the emulsification phase inversion method, the particle size can be controlled by a known method such as adding water and using a surfactant in combination for phase inversion or stirring during phase inversion.

  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)]
284 parts by weight of bisphenol, 650 parts by weight of adipic acid, and 2.5 parts by weight of titanium diisopropoxybistriethanolamate as a polymerization catalyst in a reaction vessel equipped with a stirrer, heating / cooling device, thermometer, cooling pipe and nitrogen introduction pipe The mixture was heated to 180 ° C., reacted for 4 hours while distilling off the water generated under the nitrogen stream at the same temperature, then heated to 220 ° C., and then 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, 24.6 weight part 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 with 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 254 parts by weight of 1,4 butanediol and 617 parts by weight of dodecanedioic acid were replaced with 408 parts by weight of 1,12 dodecanediol and 434 parts by weight of dodecanedioic acid in Production Example 1. Resin (A-3) was obtained.

<Comparative Production Example 1> [Synthesis of Amorphous Resin (RA-1)]
Manufactured in Production Example 1 except that 254 parts by weight of 1,4 butanediol and 617 parts by weight of dodecanedioic 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. In the same manner as in Example 1, 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-3) and the amorphous resin (RA-1).

<Production Example 4> [Synthesis of vinyl resin having ester group (LB-1)]
The autoclave was charged with 80 parts by weight of xylene and replaced with nitrogen, and then heated to 185 ° C. Next, a mixed solution of 60 parts by weight of styrene, 28 parts by weight of n-butyl methacrylate, 10 parts by weight of methyl methacrylate, 2 parts by weight of acrylic acid, 15 parts by weight of di-t-butyl peroxide and 35 parts by weight of xylene at the same temperature. The solution was added dropwise at the same temperature over 3 hours, and further kept at the same temperature for 1 hour to obtain a xylene solution of a vinyl resin (LB-1) having an ester group.

<Production Example 5> [Synthesis of vinyl resin having ester group (LB-2)]
In Production Example 4, 60 parts by weight of styrene, 28 parts by weight of n-butyl methacrylate, 10 parts by weight of methyl methacrylate, 28 parts by weight of n-butyl methacrylate, 70 parts by weight of methyl methacrylate, 2 parts by weight of acrylic acid A xylene solution of a vinyl resin (LB-2) having an ester group was obtained in the same manner as in Production Example 1 except that it was replaced with a part.

<Production Example 6> [Synthesis of vinyl resin having ester group (LB-3)]
In Production Example 4, 60 parts by weight of styrene, 28 parts by weight of n-butyl methacrylate, 10 parts by weight of methyl methacrylate, 2 parts by weight of acrylic acid, 28 parts by weight of n-butyl methacrylate, 70 parts by weight of methyl acrylate, 2 parts by weight of acrylic acid A xylene solution of a vinyl resin (LB-3) having an ester group was obtained in the same manner as in Production Example 2 except that

<Production Example 7> [Synthesis of vinyl resin having ester group (HB-1)]
After replacing the autoclave with nitrogen, 28 parts by weight of n-butyl acrylate, 70 parts by weight of methyl methacrylate and 2 parts by weight of acrylic acid were charged, and the temperature was raised to 95 ° C. over 1 hour. Next, 4 parts by weight of 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane was charged, and bulk polymerization was performed at 95 ° C. for 4 hours. 120 parts by weight of xylene was added dropwise over 1 hour. Then, it heated up to 110 degreeC over 1 hour, and hold | maintained at the same temperature for 2 hours. Further, 1.5 parts by weight of 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane was charged and polymerized for 4 hours. Thereafter, the temperature was raised to 150 ° C. over 1 hour and held at the same temperature for 1 hour, and then diluted by adding 105.5 parts by weight of xylene to obtain a xylene solution of a vinyl resin (HB-1) having an ester group.

<Production Example 8> [Synthesis of vinyl resin having ester group (HB-2)]
In Production Example 7, 28 parts by weight of n-butyl acrylate, 70 parts by weight of methyl methacrylate and 2 parts by weight of acrylic acid were replaced with 28 parts by weight of n-butyl acrylate, 70 parts by weight of methyl acrylate and 2 parts by weight of acrylic acid. Produced a xylene solution of a vinyl resin (HB-2) having an ester group in the same manner as in Production Example 5.

<Comparative Production Example 2> [Synthesis of Copolymer (RLB-1)]
In Production Example 4, Production Example 4 except that 60 parts by weight of styrene, 28 parts by weight of n-butyl methacrylate, 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. Polymerization was conducted in the same manner to obtain a xylene solution of the copolymer (RLB-1).

<Comparative Production Example 3> [Synthesis of Copolymer (RHB-2)]
In Production Example 7, polymerization was conducted in the same manner as in Production Example 7, except that 28 parts by weight of n-butyl acrylate, 70 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. A xylene solution of the copolymer (RHB-1) was obtained.

  Table 2 shows physical property values of vinyl resins (LB-1) to (LB-3), (HB-1) to (HB-2), (RLB-1), and (RLB-2) having an ester group.

<Production Examples 9 to 13><Comparative Production Examples 4 to 5>
The xylene solutions of vinyl resins having an ester group (LB-1) to (LB-3) and (HB-1) to (HB-2) were respectively charged into an autoclave and uniformly dissolved under reflux of xylene. Next, the temperature was raised to 170 ° C. while removing xylene at 1 kPa or less. It is confirmed by gas chromatography that xylene in the resin is 1,000 ppm and the monomer is 1,000 ppm or less, and vinyl resins having an ester group (TB-1) to (TB-5), (RTB-1) To (RTB-2).

  Table 3 shows physical property values of vinyl resins (TB-1) to (TB-5) and (RTB-1) to (RTB-2) having ester groups, which were obtained in the above production examples.

<Production Examples 14 to 18><Comparative Production Examples 6 to 7> [Production of Resin Solution]
In a reaction vessel equipped with a stirrer, 50 parts by weight of vinyl resins (TB-1) to (TB-5) each having an ester group and 50 parts by weight of ethyl acetate are added and stirred to dissolve the resin uniformly. Solution (TBS-1) to (TBS-5) and (RTBS-1) to (RTBS-2) were obtained.

<Production Example 19> [Production of crystalline resin dispersion (AD-1)]
Into 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 ethyl acetate were added and the temperature was raised to 78 ° C. with stirring. Warm, stir at the same temperature for 30 minutes, cool to 10 ° C. over 1 hour to crystallize the crystalline resin into fine particles, wet pulverize with Ultra Viscomil (manufactured by IMEX), (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 20> [Production of crystalline resin dispersion (AD-2)]
A crystalline resin dispersion (AD-2) was obtained in the same manner as in Production Example 19 except that 15 parts by weight of the resin (A-1) in Production Example 19 was replaced with the resin (A-2). The volume average particle diameter of (AD-2) was 0.5 μm, and the solid content concentration was 50% by weight.

<Production Example 21> [Production of crystalline resin dispersion (AD-3)]
A crystalline resin dispersion (AD-3) was obtained in the same manner as in Production Example 19 except that 15 parts by weight of the resin (A-1) was replaced with the resin (A-3) in Production Example 19. The volume average particle diameter of (AD-3) was 0.5 μm, and the solid content concentration was 50% by weight.

<Production Example 22> [Production of release agent dispersion]
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., Nippon Seiki Co., Ltd.] 10 parts by weight, ethyl acetate 15 parts by weight was added, the temperature was raised to 78 ° C. with stirring, the mixture was stirred at the same temperature for 30 minutes, cooled to 30 ° C. over 1 hour to crystallize the paraffin wax into fine particles, and Ultraviscomil (IMEX) To obtain a release agent dispersion. The obtained release agent dispersion had a volume average particle size of 0.25 μm and a solid content concentration of 50% by weight.

<Examples 1 to 7, Comparative Examples 1 to 4> [Production of Toner]
Crystalline resins (A-1) to (A-3), (RA-1) and vinyl resins having ester groups (TB-1) to (TB-5), (RTB-1) to (RTB-2) Are weighted as described in Table 3 below, and 6 parts by weight of carbon black [MA100 manufactured by Mitsubishi Kasei Co., Ltd.], paraffin wax “HNP-9” [Maximum melting heat peak temperature: 73 ° C., Nippon Seiki ( Co., Ltd.] 6 parts by weight, Henschel mixer FM10B [Mitsui Miike Chemical Co., Ltd.] and then uniformly mixed, then kneaded with a twin screw extruder [PCM30, Ikegai Co., Ltd.] with a resin temperature of 130 ° C., cooled The product was finely pulverized with a jet pulverizer [Lab Jet LJ, manufactured by Nippon Pneumatic Industry Co., Ltd.] and classified with a dispersion separator [MDS-II, manufactured by Nippon Pneumatic Industry Co., Ltd.]. Next, 99 parts by weight of the obtained toner particles, 0.5 part by weight of colloidal silica 1 (Aerosil R972, Aerosil RY50 manufactured by Nippon Aerosil) and 0.5 part by weight of colloidal silica 2 (Aerosil RY50 manufactured by Nippon Aerosil) were uniformly mixed. Thus, toners (T-1) to (T-7) of the present invention having a volume average particle diameter of 9 μm and comparative toners (RT-1) to (RT-4) were obtained.
The volume average particle diameter was measured with a Coulter counter (Multisizer TM3, manufactured by Beckman Coulter, Inc.).

<Examples 6 to 10>
Solutions (TBS-1) to (TBS-5), (RTBS-1) to (RTBS-2), (AD-1) to (AD-3) obtained in Production Examples 8 to 10 The solid content of each liquid was weighed so as to have the parts by weight shown in Table 3 below, and a toner was prepared by the following method.
In a beaker, 95 parts by weight of ion-exchanged water, 1 part by weight of sodium carboxymethylcellulose, 50.0% by weight aqueous solution of sodium dodecyl diphenyl ether disulfonate “Eleminol MON-7” [manufactured by Sanyo Chemical Industries, Ltd.] 16.8 parts by weight and 8.9 parts by weight of ethyl acetate was added and stirred to dissolve uniformly. Next, the temperature was raised to 25 ° C., and while stirring the TK auto homomixer at 10,000 rpm at the same temperature, 8.40 parts by weight of the crystalline resin dispersant (AD-1), 2.2 parts by weight of the colorant, and the mold release 4.35 parts by weight of the agent dispersion and 69.9 parts by weight of the solutions (TBS-1) to (TBS-) and (RTB-1) to (RTB-2) were added and stirred for 2 minutes. Next, this dispersion was transferred to a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling tube and a thermometer, and ethyl acetate was distilled off at 30 ° C. until the concentration reached 0.5% by weight or less. An aqueous resin 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 (T-8) to (T-14) of the present invention having a volume average particle diameter of 5 μm are uniformly mixed with 99 parts by weight of the obtained toner particles and 1.0 part by weight of colloidal silica (Aerosil R972 manufactured by Nippon Aerosil). Comparative toners (RT-5) to (RT-8) were obtained.

For toners (T-1) to (T-14) and (RT-1) to (RT-8), the monomer content and solvent content were measured by the above methods, and the low temperature fixability and gloss were measured by the following methods. , Heat resistant storage stability, moist heat resistant storage stability and durability were evaluated, and the results are shown in Table 4.
[1] Low-temperature fixability The toners (T-1) to (T-14) and (RT-1) to (RT-8) are uniformly placed on the paper 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] Gloss Using an gloss meter (VG-1D) (manufactured by Nippon Denshoku Co., Ltd.) for an image fixed at 140 ° C., adjusting the light projection angle and the light reception angle to 60 °, and switching 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 stability Toners (T-1) to (T-14) and (RT-1) to (RT-8) are allowed to stand at 50 ° C. for 1 day, and the degree of blocking is judged visually. The heat resistant storage stability was evaluated according to the following criteria.
[Evaluation criteria]
○: Blocking does not occur Δ: Blocking occurs but disperses easily when force is applied.
X: Blocking occurs [4] Humidity and heat storage stability Toners (T-1) to (T-14) and (RT-1) to (RT-8) were placed at 40 ° C. and a relative humidity of 80%. It left still for 20 hours in atmosphere, the degree of blocking was judged visually, and the heat-and-heat-resistant storage stability was evaluated on the following references | standards.
[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 Toners (T-1) to (T-14) and (RT-1) to (RT-8) are used as two-component developers, and a commercially available monochrome copying machine [AR5030, manufactured by Sharp Corporation] is used. 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 of the present invention is useful as an electrophotographic toner, an electrostatic recording toner, an electrostatic printing toner and the like because it can achieve both heat-resistant storage stability, moisture-heat storage resistance and low-temperature fixability, and has excellent toner durability and gloss. It is.

Claims (24)

  A toner containing a colorant and a binder resin, wherein the binder resin contains a crystalline resin (A) and a vinyl resin (B) having an ester group.   The toner according to claim 1, wherein an 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 according to claim 1, 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.   The toner according to claim 3, wherein the crystalline resin (A) is a crystalline resin having an ester group.   The absolute value of the difference between the ester group concentration based on the weight of (A) of the crystalline resin (A) and the ester group concentration based on the weight of (B) of the vinyl resin (B) having an ester group is 45% by weight or less. The toner according to claim 4. 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. The toner described in 1. The toner according to claim 1, wherein the toner satisfies condition 1.
[Condition 1]
1.1 ≦ (Tg1) / (Tg2) ≦ 3.5
(Tg1); 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): After Tg1 measurement by differential scanning calorimetry of the toner, when cooled from 150 ° C. to −20 ° C./min at 10 ° C./min and increased from −20 ° C. to the measurement end temperature of 150 ° C. at 10 ° C./min Detected glass transition temperature [℃]   In the molecular weight distribution obtained by gel permeation chromatography of 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 60,000 and a region having a molecular weight of 100,000 to 2,000,000. The toner according to claim 1.   The toner according to claim 1, wherein the vinyl resin (B) having an ester group is a vinyl resin having an ester group having (meth) acrylic acid ester as a structural unit.   The toner according to any one of claims 1 to 7, wherein the vinyl resin (B) having an ester group is a vinyl resin having an ester group having a styrene monomer and / or a carboxyl group-containing vinyl monomer as a structural unit.   The toner according to claim 1, wherein the monomer content in the toner is 5,000 ppm or less based on the weight of the toner.   The toner according to claim 1, wherein the solvent content in the toner is 5,000 ppm or less based on the weight of the toner. The toner according to claim 1, wherein the vinyl resin (B) having an ester group has a storage elastic modulus G ′ (120) at 120 ° C. of 1000 to 1 × 10 ⁶ [Pa · s].   The 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 toner according to claim 1, wherein the crystalline resin (A) has a weight average molecular weight of 3,000 to 50,000. The 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]
{G ′ (Ta + 10): Storage modulus [Pa · s] of (A) at (Ta + 10) [° C.],
G ′ (Ta-10): Storage modulus of [A) at (Ta-10) [° C.] [Pa · s]} The toner according to claim 1, wherein the crystalline resin (A) satisfies condition 4.
[Condition 4]
3 ≦ Log (G ′ (Ta−10)) − Log (G ′ (Ta + 10)) ≦ 8   The 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 binder resin.   The toner according to claim 1, wherein the colorant is a colorant containing one or more selected from the group consisting of a black colorant, a blue colorant, a red colorant, and a yellow colorant.   The toner according to claim 1, further comprising a release agent. 21. The toner according to claim 20, wherein the maximum temperature (Ta) of the endothermic peak of the release agent is 40 to 90 ° C., and the kinematic viscosity at 100 ° C. is 3 to 20 [mm ² / s].   The toner according to claim 20 or 21, wherein the release agent contains one or more selected from the group consisting of natural wax, petroleum wax, synthetic wax, and synthetic ester wax.   Further, the toner contains a fluidizing agent, and the fluidizing agent is a fluidizing agent 1 having a primary particle volume average particle size of 10 to 100 nm and a spherical particle having a primary particle volume average particle size of 70 to 200 nm. The toner according to claim 1, comprising the fluidizing agent 2, wherein the content of the fluidizing agent is 0.2 to 5.0% by weight based on the weight of the toner. 24. The toner according to claim 23, wherein the fluidizing agent contains at least two kinds selected from the group consisting of silica, titania, alumina, fatty acid metal salts, silicone resin particles, and fluororesin particles.