JP2014077832A - Toner binder and toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner binder that has excellent low-temperature fixability and blocking resistance, and excellent image intensity of toner and printed matters.SOLUTION: A toner binder contains a crystalline resin (A), and (A) has an ester group and has the maximum peak temperature of heat of fusion of 40 to 100°C; and the pencil hardness of the toner binder is 4B to 5H.

Description

  The present invention relates to a toner binder and a toner containing the same.

Conventionally, a technique for fixing toner with low energy is desired. Therefore, there is a strong demand for an electrostatic charge developing toner that can be fixed at a lower temperature.
As a means for lowering the toner fixing temperature, a technique for lowering the glass transition point of the toner binder is generally used. However, if the glass transition point is too low, powder aggregation (blocking) is likely to occur, and the storage stability of the toner on the surface of the fixed image is deteriorated. Therefore, the lower limit of the glass transition point is practically 50 ° C. This glass transition point is a design point of the toner binder, and it has not been possible to obtain a toner that can be fixed at a lower temperature by the method of lowering the glass transition point.
As means for achieving both blocking prevention and low-temperature fixability, a method in which a crystalline resin and an amorphous resin are used in combination as a toner binder has been proposed (Patent Documents 1 and 2).
However, such a method can ensure elasticity at the time of melting, but has a problem that the image strength of the toner or printed matter is significantly reduced.
Further, as a means for preventing blocking and achieving both toner strength and low-temperature fixability, a toner having a shell layer obtained by a melt suspension method or an emulsion aggregation method has been proposed (Patent Documents 3 and 4). . However, such a technique is still insufficient to obtain good blocking resistance while maintaining low-temperature fixing.

JP 2007-147927 A JP 2004 197051 A JP 2007-70621 A JP 2004-191927 A

  The object of the present invention is to solve the above-mentioned problems of the prior art. That is, an object of the present invention is to provide a toner binder that is excellent in low-temperature fixability and anti-blocking property and excellent in image strength of toner and printed matter, and a toner containing the toner binder.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have reached the present invention. That is, the present invention is a toner binder comprising a crystalline resin (A), wherein (A) has an ester group, and (A) has a maximum peak heat of fusion of 40 to 100 ° C., A toner binder having a pencil hardness of 4B to 5H; and a toner containing the toner binder.

  The toner containing the toner binder of the present invention is excellent in low-temperature fixability and anti-blocking property and excellent in image strength of toner and printed matter.

The toner binder of the present invention contains a crystalline resin (A).
In the present invention, “crystallinity” refers to a ratio (Tm / Ta) between the softening point of a resin (hereinafter abbreviated as Tm) and the maximum peak temperature of heat of fusion (hereinafter abbreviated as Ta) of 0.8 to 1. In DSC, it means a resin having a clear endothermic peak, not a stepwise change in endothermic amount. Tm and Ta can be measured by the following method.
<Tm measurement method>
Using a Koka flow tester {for example, “CFT-500D” [manufactured by Shimadzu Corporation]}, a 1 g measurement sample is heated at a heating rate of 6 ° C./min, and a load of 1.96 MPa is applied by a plunger. Is drawn from a nozzle having a diameter of 1 mm and a length of 1 mm, and a graph of “plunger lowering amount (flow value)” and “temperature” is drawn, corresponding to 1/2 of the maximum value of the plunger lowering amount. The temperature is read from the graph, and this value (temperature when half of the measurement sample flows out) is defined as Tm.
<Ta measurement method>
It is measured using a differential scanning calorimeter {for example, “DSC210” [manufactured by Seiko Instruments Inc.]}.
(A) used for the measurement of Ta is melted at 130 ° C. as a pretreatment, and then the temperature is lowered from 130 ° C. to 70 ° C. at a rate of 1.0 ° C./min. The temperature is lowered at a rate of ° C / min. Here, by DSC, the temperature is increased at a rate of temperature increase of 20 ° C./min and the endothermic change is measured, and a graph of “endothermic amount” and “temperature” is drawn. Let Ta ′ be the maximum peak temperature at ℃. 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′−10) ° C. for 6 hours, and then stored at (Ta′−15) ° C. for 6 hours.
Next, after the above (A) was cooled to 0 ° C. by DSC at a temperature decrease rate of 10 ° C./min, the temperature was increased at a temperature increase rate of 20 ° C./min to measure the endothermic change and draw a similar graph. The temperature corresponding to the maximum peak of heat is the maximum peak temperature (Ta) of heat of fusion.

The crystalline resin (A) in the present invention has an ester group. Examples of the crystalline resin (A) having an ester group include a crystalline polyester resin (A1), a crystalline polyurethane resin (A2), a crystalline polyurea resin (A3), and a crystalline vinyl resin (A4).
As (A), (A1) to (A4) 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) And the like.
Of these, preferred are alkene dicarboxylic acids and aromatic dicarboxylic acids, and more preferred are aromatic dicarboxylic acids.

  (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.

  Examples of the crystalline polyurethane resin (A2) include those containing the crystalline polyester resin (A1), the diol (1) and / or diamine (3), and the diisocyanate (4) as structural units.

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 (such as ethylene diamine, propylene diamine, trimethylene diamine, tetramethylene diamine and hexamethylene diamine) and polyalkylenes (having 2 to 6 carbon atoms) [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) has the diol (1 ′) as a structural unit, the chargeability and heat resistant storage stability of the toner 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 viewpoints of toner chargeability and heat-resistant storage stability. ).

  Examples of the crystalline polyurea resin (A3) include those having the crystalline polyester resin (A1), the diamine (3), and the diisocyanate (4) as structural units.

Examples of the crystalline vinyl resin (A4) include a polymer obtained by homopolymerizing or copolymerizing an ester having a polymerizable double bond.
Examples of the ester having a polymerizable double bond include vinyl acetate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl methacrylate, methyl-4-vinyl benzoate, cyclohexyl methacrylate, benzyl methacrylate, phenyl (meta ) Acrylate, vinyl methoxyacetate, vinyl benzoate, ethyl-α-ethoxy acrylate, 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) acrylate, etc.], dialkyl fumarate (two alkyl groups are straight, branched or alicyclic groups having 2 to 8 carbon atoms), dialkyl maleate (two The alkyl group is a linear, branched or alicyclic group having 2 to 8 carbon atoms), poly (meth) allyloxyalkanes (dialyloxyethane, triaryloxyethane, tetraallyloxyethane) , Tetraallyloxypropane, tetraallyloxybutane, tetrametaallyloxyethane, etc.) monomers having a polyalkylene glycol chain and a polymerizable double bond [polyethylene glycol [Mn = 300] mono (meth) acrylate, polypropylene Glycol (Mn = 500) monoacrylate, methyl alcohol EO 10 mol adduct (meth) acrylate and laur Lyl alcohol EO 30 mol adduct (meth) acrylate, etc.], poly (meth) acrylates [poly (meth) acrylate of polyhydric alcohols: ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol Di (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate and the like] and the like.

  In addition to the ester having a polymerizable double bond, the crystalline vinyl resin (A4) can contain the following monomers (5) to (13) as constituent monomers.

(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 R ¹ O may be used alone or in combination of two or more, and when two or more are used in combination, the bonding 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 is substituted with a fluorine atom; Or an alkyl group having 1 to 15 carbon atoms.

(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) 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) 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.
(13-2) C4-C12 ketone having a polymerizable double bond:
Examples include vinyl methyl ketone, vinyl ethyl ketone, and vinyl phenyl ketone.
(13-3) a sulfur-containing compound having 2 to 16 carbon atoms 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.

  Of the crystalline resins (A), the crystalline polyester resin (A1) and the crystalline polyurethane resin (A2) are preferable from the viewpoint of the adhesive strength of the toner, and more preferable among (A2) are molecules in the molecule. Have a urethane group and a urea group.

When the crystalline resin (A) has a urethane group and a urea group, the urethane group concentration of (A) based on the weight of (A) is preferably 3 to 20% by weight, more preferably 4 to 4%. 15% by weight.
The urea group concentration of (A) based on the weight of (A) is preferably 0.1 to 5.0% by weight, more preferably 0.2 to 3.0% by weight.

  (Ta) of the crystalline resin (A) is 40 to 100 ° C., and preferably 45 to 90 ° C., more preferably 50 to 80 ° C. from the viewpoint of low-temperature fixability and heat-resistant storage stability.

In the crystalline resin (A) of the present invention, the storage elastic modulus G ′ [G ′ (Ta + 20)] [Pa] at (Ta + 20) ° C. satisfies the following [Condition 1] in the viscoelasticity measurement of (A). Is preferable, and it is more preferable to satisfy [Condition 1-1].
[Condition 1] 1 × 10 ³ ≦ G ′ (Ta + 20) ≦ 1 × 10 ⁶
[Condition 1-1] 5 × 10 ³ ≦ G ′ (Ta + 20) ≦ 1 × 10 ⁵
When G ′ (Ta + 20) is in the above range, the image strength and the low-temperature fixability are good.
The crystalline resin (A) satisfying [Condition 1] and [Condition 1-1] can be obtained by adjusting the ratio of the crystalline component in (A), adjusting Mw, and the like. For example, when the ratio of the crystalline part (x) and the ratio of the crystalline component described later are increased, the value of G ′ (Ta + 20) decreases. Further, the value of G ′ (Ta + 20) is decreased by decreasing Mw of (A).

The viscoelasticity of the crystalline resin (A) can be measured using a dynamic viscoelasticity measuring apparatus “RDS-2” (Rheometric Scientific) under a frequency of 1 Hz.
Viscoelasticity measurement of (A) is carried out by setting (A) on the jig of the measuring device, raising the temperature to (Ta + 30) ° C. of (A) and bringing it into close contact with the jig, and then changing from (Ta + 30) ° C. to (Ta− 30) Decrease in temperature at a rate of 0.5 ° C./min to 30 ° C., leave at (Ta-30) ° C. for 1 hour, then decrease to (Ta-10) ° C. at a rate of 0.5 ° C./min. (Ta-10) The sample is allowed to stand at 1 ° C. for 1 hour, and after sufficiently allowing crystallization to proceed, measurement is performed using this. The measurement temperature range is 30 ° C. to 200 ° C., and by measuring the viscoelasticity between these temperatures, a temperature-G ′ curve can be obtained.

The crystalline resin (A) preferably satisfies the following condition 2. Satisfying condition 2 improves the adhesive strength of the toner binder.
[Condition 2]
5.0 ≦ 1.17 × (A-urethane) + 2.13 × (A-urea) −2.23
[(A-urethane); (A) urethane group concentration (% by weight), (A-urea); (A) urea group concentration (% by weight)]

  The lower limit in Condition 2 is preferably 5.5 from the viewpoint of the adhesive strength of the toner, and more preferably 6.0.

(A-urethane) and (A-urea) in (A) are the content of N atom quantified by a nitrogen analyzer “ANTEK7000” [manufactured by Antec Co., Ltd.] and the urethane group and urea group quantified by NMR. Calculated from the ratio.
When amine compounds are used as catalysts and / or additives during the production of (A), it is necessary to subtract them. If the boiling point of the amine compound used is less than 70 ° C, the sample should be at 130 ° C. The method of measuring after drying under reduced pressure for 2 hours is mentioned. Further, when the boiling point of the amine compound used is 70 ° C. or higher, the sample is measured as it is, and the N atom content calculated from the input amount of the amine compound is subtracted from the quantified N atom content. The method of doing is mentioned.
About NMR measurement, it can carry out by the method as described in "Structural study of polyurethane resin by NMR: Takeda Laboratory report 34 (2), 224-323 (1975)". That is, H1-NMR was measured, and the weight ratio of urea group to urethane group was measured from the ratio of the integral amount of hydrogen derived from urea groups near a chemical shift of 6 ppm and the integral amount of hydrogen derived from urethane groups near a chemical shift of 7 ppm. The urea group content and the urethane group content are calculated from the weight ratio and the N atom content.
(A-urethane) and (A-urea) can be adjusted by adjusting the composition and input amount of the raw material.

The crystalline resin (A) in the present invention is the crystalline polyester resin (A1), crystalline polyurethane resin (A2), crystalline polyurea resin (A3), crystalline vinyl resin (A4) exemplified as the above (A). ) And a crystalline part (x) selected from the composite resin, or a noncrystalline property consisting of one or more crystalline parts (x) and an amorphous resin (B). It may be a block resin having at least one part (y).
As the non-crystalline resin (B) in the present invention, the crystalline polyester resin (A1), the crystalline polyurethane resin (A2), the crystalline polyurea resin (A3), the crystal exemplified as the crystalline resin (A). Resin having the same composition as that of the conductive vinyl resin (A4) and a ratio of Tm to Ta (Tm / Ta) greater than 1.55.

In the case where the crystalline resin (A) is a block resin composed of a crystalline part (x) and an amorphous part (y), the reactivity of the terminal functional groups of (x) and (y) is considered. Then, the use or non-use of the binder is selected, and when the binder is used, the binder type suitable for the terminal functional group is selected, (x) and (y) are bonded, the block resin and can do.
When a binder is not used, the reaction between the terminal functional group (a) that forms (x) and the terminal functional group (B) that forms (y) proceeds while heating and decompressing as necessary. In particular, in the case of a reaction between an acid and an alcohol or a reaction between an acid and an amine, if the acid value of one resin is high and the hydroxyl value or amine value of the other resin is high, the reaction proceeds smoothly. The reaction temperature is preferably 180 to 230 ° C.
When binders are used, various binders can be used. Examples of the binder include the diol (1), dicarboxylic acid (2), diamine (3), diisocyanate (4), and polyepoxide.

Examples of the polyepoxide 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'-dihydroxybiphenyl di 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. ; As the alicyclic polyepoxy compound, 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-methyl (Cyclohexylmethyl) 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 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 Can be mentioned. 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, aliphatic polyepoxy compounds and aromatic polyepoxy compounds are preferred. Two or more polyepoxides may be used in combination.

Examples of the method of combining (x) and (y) include dehydration reaction and addition reaction of (x) and (y).
Examples of the dehydration reaction include a reaction in which both (x) and (y) have a hydroxyl group and these are bonded with a binder [for example, dicarboxylic acid (2)]. The dehydration reaction can be carried out at a reaction temperature of 180 to 230 ° C. without solvent.
As an addition reaction, both (x) and (y) have a hydroxyl group and these are bonded with a binder [eg, diisocyanate (4)], or one of (x) and (y) has a hydroxyl group. In the case where the other is a resin having an isocyanate group, a reaction for bonding them without using a binder can be mentioned. The addition reaction can be carried out at a reaction temperature of 80 to 150 ° C. by dissolving it in a solvent that can dissolve both (x) and (y) and adding a binder if necessary.

  When the crystalline resin (A) is a block copolymer composed of (x) and (y), the content of (x) in (A) is preferably 50 to 99% by weight. More preferably, it is 55 to 98% by weight, particularly preferably 60 to 95% by weight, and most preferably 62 to 80% by weight. When the content of (x) is in the above range, the crystallinity of (A) is not impaired, and the low-temperature fixability, storage stability, and gloss of the toner are favorable.

The toner binder of the present invention has a pencil hardness of 4B to 5H, and preferably 3B to 4H from the viewpoint of toner strength. The pencil hardness of the toner binder can be measured by the following method.
<Measuring method of pencil hardness of toner binder>
In accordance with JIS K5600, a scratch test is performed on the toner binder by applying a load of 10 g from right above the pencil fixed at an angle of 45 degrees, and the pencil hardness that does not damage the toner binder is defined as the pencil hardness.

From the viewpoint of heat-resistant storage stability, the crystalline resin (A) preferably has a heat of fusion of 20 to 90 J / g, more preferably 30 to 80 J / g, and particularly preferably 35 to 75 J / g.
The heat of fusion of (A) can be measured by the following method.
<Measuring method of heat of fusion of (A)>
A differential scanning calorimeter “DSC Q1000” (manufactured by TA Instruments) is used for measurement under the following conditions.
Temperature increase rate: 10 ° C / min
Measurement start temperature: 20 ° C
Measurement end temperature: 180 ° C
The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium.
Specifically, (A) about 5 mg is precisely weighed and placed in a silver pan, and the endothermic measurement is performed once to obtain a DSC curve. The heat of fusion is determined from this DSC curve. A silver empty pan is used as a reference.

The Mn of the crystalline resin (A) is preferably 1,000 to 5,000,000, more preferably 2,000 to 500,000.
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 solubility parameter (hereinafter abbreviated as SP value) of the crystalline resin (A) is preferably 7 to 18 (cal / cm ³ ) ^1/2 , and more preferably 8 to 16 (cal / cm ³ ). ^1/2 , particularly preferably 9 to 14 (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 glass transition temperature (hereinafter abbreviated as Tg) of the crystalline resin (A) is preferably 20 to 200 ° C, more preferably 40 ° C to 150 ° C. In addition, Tg can be measured by the method (DSC) prescribed | regulated to ASTM D3418-82 using "DSC20, SSC / 580" [made by Seiko Instruments Inc.].

In the toner binder of the present invention, the crystalline resin (A) may be used alone, or the above-mentioned amorphous resin (B) may be used in combination with (A).
The content of the crystalline resin (A) in the toner binder is preferably 51% by weight, more preferably 60% by weight or more, and particularly preferably 70% by weight or more based on the weight of the toner binder.

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

  As the colorant, all of dyes and pigments used as toner colorants can be used. Specifically, carbon black, iron black, Sudan black SM, first yellow G, benzidine yellow, solvent yellow (21, 77, 114, etc.), pigment yellow (12, 14, 17, 83, etc.), Indian first orange, Irgasin Red, Paranitonianiline Red, Toluidine Red, Solvent Red (17, 49, 128, 5, 13, 22 and 48.2, etc.), Disperse Red, Carmine FB, Pigment Orange R, Lake Red 2G, Rhodamine FB, Rhodamine B lake, methyl violet B lake, phthalocyanine blue, solvent blue (25, 94, 60, 15.3, etc.), pigment blue, brilliant green, phthalocyanine green, oil yellow GG, Kayaset YG, o Tetrazole brown B and oil pink OP, and the like. These may be used alone or in admixture of two or more. Further, if necessary, a magnetic powder (a powder of a ferromagnetic metal such as iron, cobalt and nickel, a compound such as magnetite, hematite and ferrite) can also be contained to serve as a colorant. The content of the colorant is preferably 0.1 to 40 parts by weight, and more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the toner binder. In addition, when using magnetic powder, Preferably it is 20-150 weight part, More preferably, it is 40-120 weight part.

As the mold release agent, those having a softening point of 50 to 170 ° C. are preferable, polyolefin wax, natural wax (for example, carnauba wax, montan wax, paraffin wax and rice wax), aliphatic alcohol having 30 to 50 carbon atoms ( For example, triacontanol etc.), fatty acids having 30 to 50 carbon atoms (e.g. triacontane carboxylic acid etc.) and mixtures thereof.
Polyolefin waxes include (co) polymers [obtained by (co) polymerization] of olefins (for example, ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-dodecene, 1-octadecene, and mixtures thereof). And olefin (co) polymer oxides by oxygen and / or ozone, maleic acid modifications of olefin (co) polymers [eg maleic acid and its derivatives (maleic anhydride, Modified products such as monomethyl maleate, monobutyl maleate and dimethyl maleate), olefins and unsaturated carboxylic acids [(meth) acrylic acid, itaconic acid and maleic anhydride, etc.] and / or unsaturated carboxylic acid alkyl esters [(meta ) Alkyl acrylate (alkyl of 1 to 18 carbon atoms) ester and Copolymers with alkyl oleates (alkyl 1 to 18 carbon atoms of esters), etc., polymethylene (eg Fischer-Tropsch wax such as sazol wax), fatty acid metal salts (eg calcium stearate) and fatty acid esters (behenic acid) Behenyl and the like).

  As charge control agents, nigrosine dyes, triphenylmethane dyes containing tertiary amines as side chains, quaternary ammonium salts, polyamine resins, imidazole derivatives, quaternary ammonium base-containing polymers, metal-containing azo dyes, copper phthalocyanine dyes , Salicylic acid metal salts, boron complexes of benzylic acid, sulfonic acid group-containing polymers, fluorine-containing polymers, halogen-substituted aromatic ring-containing polymers, metal complexes of salicylic acid alkyl derivatives, cetyltrimethylammonium bromide, and the like.

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

The content of each component constituting the toner of the present invention is as follows.
The content of the toner binder 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 to 60% by weight, more preferably 0.1 to 40% by weight, and particularly preferably 0.5 to 30% 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 0.5 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 to 5% by weight, and particularly preferably 0.1 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. Further, instead of carrier particles, an electric latent image can be formed by rubbing with a charging blade or the like, and the electric latent image can be formed on a support (paper, polyester film, etc.) by a known heat roll fixing method. ).

The volume average particle diameter (hereinafter abbreviated as D50) of the toner of the present invention is preferably 1 to 15 μm, more preferably 2 to 10 μm, and particularly preferably 3 to 7 μm.
The volume average particle diameter of the toner of the present invention 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. . Moreover, you may manufacture by the method of using the organic microparticles of Unexamined-Japanese-Patent No. 2002-284881.

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

<Production Example 1> [Synthesis of Crystalline Polyester Resin (A1-1)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling tube, a thermometer, and a nitrogen introduction tube, 648.9 parts by weight of sebacic acid, 464.6 parts by weight of 1,6-hexanediol, and titanium dihydroxybis as a condensation catalyst 1 part by weight of (triethanolaminate) is added, the temperature is raised to 180 ° C., the reaction is carried out for 10 hours while distilling off the water produced under a nitrogen stream at the same temperature, and then gradually raised to 220 ° C. The reaction is carried out for 4 hours while distilling off the water generated under a nitrogen stream, and further the reaction is carried out while distilling off the water under a reduced pressure of 0.007 to 0.026 MPa. When the acid value becomes 2 or less, the product is taken out. Crystalline polyester resin (A1-1) was obtained. The melting point of (A1-1) was 63 ° C., Mw was 5,000, and the hydroxyl value was 82.

<Production Example 2> [Synthesis of Crystalline Polyester Resin (A1-2)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling tube, a thermometer, and a nitrogen introduction tube, 685.5 parts by weight of sebacic acid, 434.6 parts by weight of 1,6-hexanediol, and titanium dihydroxybis as a condensation catalyst 1 part by weight of (triethanolaminate) is added, the temperature is raised to 180 ° C., the reaction is carried out for 10 hours while distilling off the water produced under a nitrogen stream at the same temperature, and then gradually raised to 220 ° C. The reaction is carried out for 4 hours while distilling off the water generated under a nitrogen stream, and further the reaction is carried out while distilling off the water under a reduced pressure of 0.007 to 0.026 MPa. When the acid value becomes 2 or less, the product is taken out. Crystalline polyester resin (A1-2) was obtained. The melting point of (A1-2) was 67 ° C., Mw was 12,000, and the hydroxyl value was 33.

<Production Example 3> [Synthesis of Crystalline Polyester Resin (A1-3)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling tube, a thermometer and a nitrogen introduction tube, 700.4 parts by weight of sebacic acid, 422.3 parts by weight of 1,6-hexanediol, and titanium dihydroxybis as a condensation catalyst 1 part by weight of (triethanolaminate) is added, the temperature is raised to 180 ° C., the reaction is carried out for 10 hours while distilling off the water produced under a nitrogen stream at the same temperature, and then gradually raised to 220 ° C. The reaction is carried out for 4 hours while distilling off the water generated under a nitrogen stream, and further the reaction is carried out while distilling off the water under a reduced pressure of 0.007 to 0.026 MPa. When the acid value becomes 2 or less, the product is taken out. Crystalline polyester resin (A1-3) was obtained. The melting point of (A1-3) was 68 ° C., Mw was 26,000, and the hydroxyl value was 13.

<Production Example 4> [Synthesis of Crystalline Polyester Resin (A1-4)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling tube, a thermometer, and a nitrogen introduction tube, 868.2 parts by weight of sebacic acid, 532.3 parts by weight of ethylene glycol, and titanium dihydroxybis (triethanolamine) as a condensation catalyst were used. Nate) 1 part by weight was charged, heated to 180 ° C., reacted for 10 hours while distilling off the water generated in the nitrogen stream at the same temperature, and then gradually heated to 220 ° C. under a nitrogen stream. The reaction is carried out for 4 hours while distilling off the produced water and ethylene glycol, and further, the reaction is carried out while distilling off water and ethylene glycol under a reduced pressure of 0.007 to 0.026 MPa. When Mw reaches 11,000. The crystalline polyester resin (A1-4) was obtained by taking out. The melting point of (A1-4) was 76 ° C., Mw was 11,000, and the hydroxyl value was 34.

<Production Example 5> [Synthesis of Crystalline Polyester Resin (A1-5)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling tube, a thermometer, and a nitrogen introduction tube, 763.1 parts by weight of sebacic acid, 509.3 parts by weight of 1,4-butanediol, and titanium dihydroxybis as a condensation catalyst 1 part by weight of (triethanolaminate) is added, the temperature is raised to 180 ° C., the reaction is carried out for 10 hours while distilling off the water produced under a nitrogen stream at the same temperature, and then gradually raised to 220 ° C. The reaction is carried out for 4 hours while distilling off water and 1,4-butanediol generated under a nitrogen stream, and further while distilling off water and 1,4-butanediol under a reduced pressure of 0.007 to 0.026 MPa. The crystalline polyester resin (A1-5) was obtained by taking it out when the Mw reached 10,000. (A1-5) had a melting point of 61 ° C., Mw of 10,000, and a hydroxyl value of 39.

<Production Example 6> [Synthesis of Crystalline Polyester Resin (A1-6)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling tube, a thermometer and a nitrogen introduction tube, 881.0 parts by weight of dodecanedioic acid, 474.8 parts by weight of ethylene glycol, and titanium dihydroxybis (triethanol as a condensation catalyst) Aminate) 1 part by weight was added, heated to 180 ° C., reacted for 10 hours while distilling off the water generated in the nitrogen stream at the same temperature, and then gradually heated to 220 ° C. under a nitrogen stream. The reaction is carried out for 4 hours while distilling off the water and ethylene glycol produced in the above, and further the reaction is carried out while distilling off the water and ethylene glycol under a reduced pressure of 0.007 to 0.026 MPa, when the Mw becomes 12,000. To obtain a crystalline polyester resin (A1-6). The melting point of (A1-6) was 85 ° C., Mw was 12,000, and the hydroxyl value was 31.

<Production Example 7> [Synthesis of Crystalline Polyester Resin (A1-7)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling tube, a thermometer, and a nitrogen introduction tube, 831.7 parts by weight of adipic acid, 706.4 parts by weight of ethylene glycol, and titanium dihydroxybis (triethanolamine) as a condensation catalyst. Nate) 1 part by weight was charged, heated to 180 ° C., reacted for 10 hours while distilling off the water generated in the nitrogen stream at the same temperature, and then gradually heated to 220 ° C. under a nitrogen stream. The reaction is carried out for 4 hours while distilling off the generated water and ethylene glycol, and further, the reaction is carried out while distilling off water and ethylene glycol under a reduced pressure of 0.007 to 0.026 MPa. When Mw reaches 12,000. The crystalline polyester resin (A1-7) was obtained by taking out. (A1-7) had a melting point of 49 ° C., Mw of 12,000, and a hydroxyl value of 33.

<Production Example 8> [Synthesis of Crystalline Polyester Resin (A1-8)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling tube, a thermometer, and a nitrogen introduction tube, 696.4 parts by weight of sebacic acid, 167.6 parts by weight of adipic acid, 569.3 parts by weight of ethylene glycol, and a condensation catalyst 1 part by weight of titanium dihydroxybis (triethanolaminate) is added, heated to 180 ° C., reacted for 10 hours while distilling off the water generated under a nitrogen stream at the same temperature, and gradually increased to 220 ° C. The reaction was carried out for 4 hours while distilling off the water and ethylene glycol produced under a nitrogen stream while raising the temperature, and the reaction was conducted while distilling off the water and ethylene glycol under a reduced pressure of 0.007 to 0.026 MPa. When it became 4,200, it took out and obtained the crystalline polyester resin (A1-8). (A1-8) had a melting point of 62 ° C., Mw of 4,200, and a hydroxyl value of 78.

<Production Example 9> [Synthesis of Crystalline Polyester Resin (A1-9)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling tube, a thermometer, and a nitrogen introducing tube, 656.2 parts by weight of sebacic acid, 335.4 parts by weight of 1,6-hexanediol, 123 of 1,3-propanediol .3 parts by weight and 1 part by weight of titanium dihydroxybis (triethanolaminate) as a condensation catalyst, heated to 180 ° C., and reacted for 10 hours while distilling off the water generated under a nitrogen stream at the same temperature. Next, water is generated under a nitrogen stream while gradually raising the temperature to 220 ° C. and allowed to react for 4 hours while distilling 1,3-propanediol, and further under reduced pressure of 0.007 to 0.026 MPa. The reaction was conducted while distilling off 1,3-propanediol, and when Mw reached 12,700, the reaction product was taken out to obtain a crystalline polyester resin (A1-9). (A1-9) had a melting point of 57 ° C., Mw of 12,700, and a hydroxyl value of 29.

<Production Example 10> [Synthesis of Crystalline Polyester Resin (A1-10)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling tube, a thermometer and a nitrogen introduction tube, 641.6 parts by weight of sebacic acid, 327.9 parts by weight of 1,6-hexanediol, 142 of 1,4-butanediol 142 .8 parts by weight and 1 part by weight of titanium dihydroxybis (triethanolaminate) as a condensation catalyst, heated to 180 ° C., and reacted for 10 hours while distilling off the water generated under a nitrogen stream at the same temperature. Next, the water produced under a nitrogen stream is reacted for 4 hours while distilling off 1,4-butanediol while gradually raising the temperature to 220 ° C., and further under reduced pressure of 0.007 to 0.026 MPa. The reaction was conducted while distilling off 1,4-butanediol, and when Mw reached 14,200, the reaction product was taken out to obtain a crystalline polyester resin (A1-10). (A1-10) had a melting point of 60 ° C., Mw of 14,200, and a hydroxyl value of 26.

<Production Example 11> [Synthesis of Crystalline Polyester Resin (A′1-1)]
In a reaction vessel equipped with a stirrer, heating / cooling device, cooling tube, thermometer and nitrogen introduction tube, 700.4 parts by weight of terephthalic acid, 422.3 parts by weight of 1,6-hexanediol, and titanium dihydroxybis as a condensation catalyst 1 part by weight of (triethanolaminate) is added, the temperature is raised to 180 ° C., the reaction is carried out for 10 hours while distilling off the water produced under a nitrogen stream at the same temperature, and then gradually raised to 220 ° C. The reaction is carried out for 4 hours while distilling off the water generated under a nitrogen stream, and further the reaction is carried out while distilling off the water under a reduced pressure of 0.007 to 0.026 MPa. When the acid value becomes 2 or less, the product is taken out. Crystalline polyester resin (A′1-1) was obtained. (A′1-1) had a melting point of 131 ° C., Mw of 12,000, and a hydroxyl value of 30.

<Production Example 12> [Synthesis of Amorphous Polyester Resin (B-1)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling tube, a thermometer, and a nitrogen introduction tube, 117.7 parts by weight of a bisphenol A / PO2 molar adduct, 626.6 parts by weight of a bisphenol A / EO2 molar adduct, isophthalate 238.9 parts by weight of acid, 43.0 parts by weight of adipic acid and 1 part by weight of dibutyltin oxide as a condensation catalyst were added, the temperature was raised to 230 ° C. at normal pressure, and the reaction was carried out at the same temperature for 5 hours. The reaction was carried out under a reduced pressure of ˜0.026 MPa for 2 hours. Subsequently, it cooled to 180 degreeC, 35.8 weight part of trimellitic anhydride was added, and it cooled to room temperature after reacting for 2 hours under normal pressure sealing, and obtained amorphous polyester resin (B-1). Tg of (B-1) was 50 ° C., Mw was 7,000, and the hydroxyl value was 50.

<Production Example 13> [Synthesis of Amorphous Polyester Resin (B-2)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling pipe, a thermometer, and a nitrogen introduction pipe, 115.3 parts by weight of a bisphenol A / PO2 molar adduct, 614.0 parts by weight of a bisphenol A / EO2 molar adduct, isophthalate 188.2 parts by weight of acid, 119.9 parts by weight of adipic acid and 1 part by weight of dibutyltin oxide as a condensation catalyst were added, the temperature was raised to 230 ° C. at normal pressure, and the reaction was continued at the same temperature for 5 hours. The reaction was carried out under a reduced pressure of ˜0.026 MPa for 2 hours. Next, the mixture was cooled to 180 ° C., 32.3 parts by weight of trimellitic anhydride was added, reacted for 2 hours under normal pressure sealing, and then cooled to room temperature to obtain an amorphous polyester resin (B-2). Tg of (B-2) was 50 ° C., Mw was 12,000, and the hydroxyl value was 20.

  Table 1 shows the compositions of the resins (A1-1) to (A1-10), (A′1-1), and (B-1) to (B-2) obtained in Production Examples 1 to 13.

<Production Example 14> [Production of crystalline polyurethane resin (A2-1)]
Into a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling tube and a thermometer, 40.7 parts by weight of 1,2-propylene glycol and 169.6 parts by weight of ethyl acetate were charged, and the water content in this solution was 0. Water was added so as to be 0.04% by weight. To this solution, 130 parts by weight of isophorone diisocyanate was added and reacted at 90 ° C. for 15 hours to obtain an amorphous polyurethane resin (B-3) having an isocyanate group at the terminal.
In another reaction vessel equipped with a stirrer, a heating / cooling device, a cooling tube and a thermometer, 325.9 parts by weight of (A1-1) and 325.9 parts by weight of ethyl acetate were added, and the temperature was raised to 70 ° C. After stirring and dissolving at the same temperature for 2 hours, water was added so that the amount of water in the solution was 0.04% by weight. After confirming dissolution, 347.9 parts by weight of (B-3) was added, the temperature was raised to 90 ° C., and the mixture was reacted at the same temperature for 15 hours. Then, ethyl acetate was removed, and a crystalline polyurethane resin (A2-1) was obtained. ) (A2-1) is composed of a crystalline part (x-1) made of (A1-1) and an amorphous part (y-1) made of (B-3).

<Production Example 15> [Production of crystalline polyurethane resin (A2-2)]
40.7 parts by weight of 1,2-propylene glycol and 169.6 parts by weight of methyl ethyl ketone were charged into a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling pipe and a thermometer. Water was added so as to be 04% by weight. To this solution, 130 parts by weight of isophorone diisocyanate was added and reacted at 90 ° C. for 15 hours to obtain an amorphous polyurethane resin (B-4) having an isocyanate group at the terminal.
(A1-2) 325.9 parts by weight and methyl ethyl ketone 325.9 parts by weight were charged into another reaction vessel equipped with a stirrer, a heating / cooling device, a cooling pipe and a thermometer, and the temperature was raised to 70 ° C. After stirring at temperature for 2 hours to dissolve, water was added so that the amount of water in this solution was 0.04% by weight. After confirming dissolution, 347.9 parts by weight of (B-4) was added, the temperature was raised to 90 ° C., and the mixture was reacted at the same temperature for 15 hours. Then, methyl ethyl ketone was removed, and crystalline polyurethane resin (A2-2) Got. (A2-2) is composed of a crystalline part (x-2) made of (A1-2) and an amorphous part (y-2) made of (B-4).

<Production Example 16> [Production of crystalline polyurethane resin (A2-3)]
Into a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling pipe, and a thermometer, 40.7 parts by weight of 1,2-propylene glycol and 169.6 parts by weight of tetrahydrofuran were added. Water was added so as to be 04% by weight. To this solution, 130 parts by weight of isophorone diisocyanate was added and reacted at 90 ° C. for 15 hours to obtain an amorphous polyurethane resin (B-5) having an isocyanate group at the terminal.
In another reaction vessel equipped with a stirrer, a heating / cooling device, a cooling tube and a thermometer, 325.9 parts by weight of (A1-3) and 325.9 parts by weight of tetrahydrofuran were added, and the temperature was raised to 70 ° C. After stirring at temperature for 2 hours to dissolve, water was added so that the amount of water in this solution was 0.04% by weight. After confirming the dissolution, 347.9 parts by weight of (B-5) was added, the temperature was raised to 90 ° C., and the mixture was reacted at the same temperature for 15 hours. Then, tetrahydrofuran was removed, and the crystalline polyurethane resin (A2-3) Got. (A2-3) is composed of a crystalline part (x-3) made of (A1-3) and an amorphous part (y-3) made of (B-5).

<Production Example 17> [Production of crystalline polyurethane resin (A2-4)]
Into a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling tube and a thermometer, 20.9 parts by weight of 1,2-propylene glycol and 276.9 parts by weight of ethyl acetate were added, and the water content in this solution was 0. Water was added so that it might become 0.07 weight%. To this solution, 48.3 parts by weight of hexamethylene diisocyanate was added and reacted at 80 ° C. for 5 hours to obtain an amorphous polyurethane resin (B-6) having an isocyanate group at the terminal.
In another reaction vessel equipped with a stirrer, a heating / cooling device, a cooling pipe and a thermometer, 325.9 parts by weight of (A1-4) and 325.9 parts by weight of ethyl acetate were added, and the temperature was raised to 70 ° C. After stirring for 2 hours at the same temperature for dissolution, water was added so that the amount of water in the solution was 0.1% by weight. After confirming the dissolution, 347.9 parts by weight of (B-6) was added, the temperature was raised to 80 ° C., and the mixture was reacted at the same temperature for 5 hours. Then, ethyl acetate was removed, and the crystalline polyurethane resin (A2-4 ) (A2-4) is composed of a crystalline part (x-4) made of (A1-4) and an amorphous part (y-4) made of (B-6).

<Production Example 18> [Production of crystalline polyurethane resin (A2-5)]
While introducing nitrogen into a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube and a decompression device, 325.9 parts by weight of crystalline polyester (A1-5), 93.9 parts by weight of bisphenol A / PO2 molar adduct Then, 498.6 parts by weight of ethyl acetate was added, the temperature was raised to 70 ° C., and the mixture was stirred at the same temperature for 2 hours to dissolve, then water was added so that the water content in the solution was 0.09% by weight. added. To this solution, 178.7 parts by weight of 4,4′-diphenylmethane diisocyanate was added, heated to 80 ° C., reacted for 5 hours, and then ethyl acetate was removed to obtain a crystalline polyurethane resin (A2-5). . (A2-5) is composed of only the crystalline part (x-5) composed of (A2-5).

<Production Example 19> [Production of crystalline polyurethane resin (A2-6)]
While introducing nitrogen into a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube and a decompression device, 374.9 parts by weight of crystalline polyester (A1-6), 2,4.1 weight of 2,2-dimethylolpropionic acid After adding 499.4 parts by weight of methyl ethyl ketone, the mixture was heated to 70 ° C. and stirred for 2 hours at the same temperature to dissolve, and then water was added so that the water content in the solution was 0.09% by weight. added. To this solution, 81.4 parts by weight of isophorone diisocyanate was added, the temperature was raised to 90 ° C., and the mixture was reacted for 20 hours. Then, methyl ethyl ketone was removed to obtain a crystalline polyurethane resin (A2-6). (A2-6) is composed of only the crystalline part (x-6) composed of (A2-6).

<Production Example 20> [Production of crystalline polyurethane resin (A2-7)]
Into a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling pipe and a thermometer, 38.7 parts by weight of 1,4-cyclohexanedimethanol and 99.5 parts by weight of tetrahydrofuran were added, and the water content in this solution was 0 Water was added so that it might become 0.07 weight%. 62.1 parts by weight of xylylene diisocyanate was added to this solution and reacted at 80 ° C. for 5 hours to obtain an amorphous polyurethane resin (B-7) having an isocyanate group at the terminal.
In a separate reaction vessel equipped with a stirrer, heating / cooling device, cooling pipe and thermometer, (A1-7) 399.9 parts by weight and tetrahydrofuran 399.9 parts by weight were charged, and the temperature was raised to 70 ° C. After stirring at temperature for 2 hours to dissolve, water was added so that the water content in this solution was 0.11% by weight. After confirming the dissolution, 347.9 parts by weight of (B-7) was added, the temperature was raised to 80 ° C., and the mixture was reacted at the same temperature for 3 hours. Then, tetrahydrofuran was removed, and the crystalline polyurethane resin (A2-7) Got. (A2-7) is composed of a crystalline part (x-7) made of (A1-7) and an amorphous part (y-5) made of (B-7).

<Production Example 21> [Production of crystalline polyurethane resin (A2-8)]
While introducing nitrogen, 446.2 parts by weight of crystalline polyester (A1-8) and 500.0 parts by weight of ethyl acetate were charged into a reaction vessel equipped with a stirrer, a thermometer, a nitrogen inlet tube and a decompressor. The solution was heated to 0 ° C. and stirred at the same temperature for 2 hours for dissolution, and then water was added so that the water content in the solution was 0.1% by weight. To this solution, 52.7 parts by weight of hexamethylene diisocyanate was added, the temperature was raised to 80 ° C., and the mixture was reacted at the same temperature for 5 hours. Then, ethyl acetate was removed to obtain a crystalline polyurethane resin (A2-8). (A2-8) is composed of only the crystalline part (x-8) composed of (A2-8).

<Production Example 22> [Production of crystalline polyurethane resin (A2-9)]
While introducing nitrogen, 483.3 parts by weight of crystalline polyester (A1-9) and 500.0 parts by weight of ethyl acetate were charged into a reaction vessel equipped with a stirrer, a thermometer, a nitrogen inlet tube and a decompressor. The temperature was raised to 0 ° C., and the mixture was stirred and dissolved at the same temperature for 2 hours, and then water was added so that the water content in the solution was 0.22% by weight. To this solution, 27.3 parts by weight of hexamethylene diisocyanate was added, the temperature was raised to 80 ° C., and the mixture was reacted at the same temperature for 5 hours. Then, ethyl acetate was removed to obtain a crystalline polyurethane resin (A2-9). (A2-9) is composed of only the crystalline part (x-9) composed of (A2-9).

<Production Example 23> [Production of crystalline polyurethane resin (A2-10)]
While introducing nitrogen, 471.5 parts by weight of crystalline polyester (A1-10) and 500.0 parts by weight of tetrahydrofuran were introduced into a reaction vessel equipped with a stirrer, a thermometer, a nitrogen inlet tube and a decompressor, and 70 ° C. The solution was stirred for 2 hours at the same temperature and dissolved, and then water was added so that the water content in the solution was 0.23% by weight. To this solution, 26.3 parts by weight of hexamethylene diisocyanate was added, the temperature was raised to 80 ° C., and the mixture was reacted at the same temperature for 5 hours. Then, tetrahydrofuran was removed to obtain a crystalline polyurethane resin (A2-10). (A2-10) is composed of only the crystalline part (x-10) composed of (A2-10).

<Production Example 24> [Production of crystalline polyurethane resin (A2-11)]
While introducing nitrogen into a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube and a decompression device, 325.4 parts by weight of crystalline polyester (A1-11), amorphous polyester (A1-11) 109.0 After adding 50 parts by weight of tetrahydrofuran and 500.0 parts by weight of tetrahydrofuran, the mixture was heated to 70 ° C. and stirred at the same temperature for 2 hours to dissolve, and then the water was adjusted so that the water content in the solution was 0.05% by weight. Was added. To this solution, 65.1 parts by weight of 4,4′-diphenylmethane diisocyanate was added, the temperature was raised to 80 ° C., the reaction was carried out at the same temperature for 5 hours, tetrahydrofuran was removed, and crystalline polyurethane resin (A2-11) was removed. Obtained. (A2-11) is composed of only the crystalline part (x-11) made of (A2-11).

<Production Example 25> [Production of crystalline polyurethane resin (A2-12)]
Into a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling pipe and a thermometer, 22.2 parts by weight of 1,2-propylene glycol and 99.5 parts by weight of ethyl acetate were added, and the water content in this solution was 0. Water was added so that it might become 0.07 weight%. To this solution, 78.4 parts by weight of isophorone diisocyanate was added and reacted at 90 ° C. for 15 hours to obtain an amorphous crystalline polyurethane resin (B-8) having an isocyanate group at the terminal.
In another reaction vessel equipped with a stirrer, a heating / cooling device, a cooling pipe and a thermometer, 325.9 parts by weight of (A1-2) and 399.9 parts by weight of ethyl acetate were charged, and the temperature was raised to 70 ° C. After stirring and dissolving at the same temperature for 2 hours, water was added so that the amount of water in the solution was 0.10% by weight. After confirming the dissolution, 200 parts by weight of (B-8) was added, the temperature was raised to 90 ° C., and the mixture was reacted at the same temperature for 15 hours. Then, ethyl acetate was removed, and the crystalline polyurethane resin (A2-12) was removed. Obtained. (A2-12) is composed of a crystalline part (x-2) composed of (A1-2) and an amorphous part (y-6) composed of (B-8).

<Production Example 26> [Production of crystalline polyurethane resin (A2-13)]
Into a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling pipe and a thermometer, 146.5 parts by weight of a bisphenol A / PO2 molar adduct and 247.9 parts by weight of ethyl acetate were added. Water was added so that it might become 0.09 weight%. To this solution, 105.5 parts by weight of isophorone diisocyanate was added and reacted at 90 ° C. for 15 hours to obtain an amorphous polyurethane resin (B-9) having an isocyanate group at the terminal.
In another reaction vessel equipped with a stirrer, a heating / cooling device, a cooling pipe and a thermometer, 250.0 parts by weight of (A1-2) and 250.0 parts by weight of ethyl acetate were charged, and the temperature was raised to 70 ° C. After stirring and dissolving at the same temperature for 2 hours, water was added so that the water content in the solution was 0.10% by weight. After confirming dissolution, 200 parts by weight of (B-9) was added, the temperature was raised to 90 ° C., and the mixture was reacted at the same temperature for 15 hours. Then, ethyl acetate was removed, and crystalline polyurethane resin (A2-13) was removed. Obtained. (A2-13) is composed of a crystalline part (x-2) composed of (A1-2) and an amorphous part (y-7) composed of (B-9).

<Production Example 27> [Production of crystalline polyurethane resin (A′2-1)]
While introducing nitrogen, 477.1 parts by weight of a crystalline polyester resin (A1-2) and 500.0 parts by weight of ethyl acetate were charged into a reaction vessel equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a decompressor. The temperature was raised to 70 ° C., and the mixture was stirred and dissolved at the same temperature for 2 hours, and then water was added so that the water content in the solution was 0.02 wt%. To this solution, 22.9 parts by weight of 4,4′-diphenylmethane diisocyanate was added, the temperature was raised to 80 ° C., and the mixture was reacted at the same temperature for 5 hours. Then, ethyl acetate was removed, and a crystalline polyurethane resin (A′2- 1) was obtained.
Table 2 shows the physical properties of the crystalline urethane resins (A2-1) to (A2-13) and (A′2-1) obtained in Production Examples 14 to 27.

<Examples 1-10, Comparative Examples 1-3>
Crystalline urethane resins (A2-1) to (A2-13), (A′2-1), and crystalline polyester resin (A′1-1) were blended according to the blending ratio (parts by weight) shown in Table 3, and crystals Toner binders (R-1) to (R-13), (R'-1) composed of conductive resins (A-1) to (A-13) and (A'-1) to (A'-3) ) To (R′-3) were obtained.

<Production Example 28> [Production of fine particle dispersion 1]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling tube and a nitrogen introduction tube, 690.0 parts by weight of water, sodium salt of ethylene oxide methacrylate adduct sulfate “ELEMINOL RS-30” [Sanyo Kasei Industrial Co., Ltd.] 9.0 parts by weight, 90.0 parts by weight of styrene, 90.0 parts by weight of methacrylic acid, 110.0 parts by weight of butyl acrylate and 1.0 part by weight of ammonium persulfate were charged at 350 rpm. When stirring for 15 minutes, a white emulsion was obtained. Next, the temperature was raised to 75 ° C., and the reaction was carried out at the same temperature for 5 hours. Further, 30 parts by weight of a 1% by weight aqueous ammonium persulfate solution was added, and the mixture was aged at 75 ° C. for 5 hours to give a vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). [Fine particle dispersion 1] was obtained. The volume average particle diameter of the particles dispersed in the fine particle dispersion 1 was measured using a laser diffraction / scattering particle size distribution measuring apparatus “LA-920” (manufactured by Horiba, Ltd.), and 0.1 μm. Met. A part of [Fine Particle Dispersion 1] was taken out and Tg and Mw were measured. As a result, Tg was 65 ° C. and Mw was 150,000.

<Production Example 29> [Production of fine particle dispersion 2]
Into a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling tube, a dropping funnel and a nitrogen introducing tube, 500 parts by weight of toluene was charged, and 350 parts by weight of toluene, “Blemmer VA” was placed in another glass beaker. [Behenyl acrylate, manufactured by NOF Corporation]] 150 parts by weight, 7.5 parts by weight of azobisisobutyronitrile (AIBN) were added, and stirred and mixed at 20 ° C. to prepare a monomer solution. It was put into a dropping funnel. After substituting the gas phase portion of the reaction vessel with nitrogen, the monomer solution was added dropwise at 80 ° C. over 2 hours in a sealed state, and after aging at 85 ° C. for 2 hours from the end of the addition, toluene was added at 130 ° C. for 3 hours. The pressure was reduced (0.007 to 0.026 MPa) to obtain an acrylic crystalline resin. The melting point of this resin was 65 ° C. and the number average molecular weight was 50,000.
After mixing 700 parts by weight of normal hexane and 300 parts by weight of the above-mentioned acrylic crystalline resin, zirconia beads having a particle diameter of 0.3 mm were used in a bead mill “Dynomill Multilab” [manufactured by Shinmaru Enterprises Co., Ltd.] The mixture was pulverized to obtain milky white [fine particle dispersion 2]. The volume average particle diameter of this dispersion was 0.3 μm.

<Production Example 30> [Production of Colorant Dispersion]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling tube, and a nitrogen introduction tube, 557 parts by weight of propylene glycol (17.5 moles), 569 parts by weight of dimethyl terephthalate (7.0 moles) Then, 184 parts by weight (3.0 parts by mole) of adipic acid and 3 parts by weight of tetrabutoxy titanate as a condensation catalyst were added, and the reaction was performed at 180 ° C. for 8 hours while distilling off the produced methanol. Next, while gradually raising the temperature to 230 ° C., the reaction was performed for 4 hours while distilling off the produced propylene glycol and water under a nitrogen stream, and the reaction was further performed for 1 hour under a reduced pressure of 0.007 to 0.026 MPa. The recovered propylene glycol was 175 parts by weight (5.5 mole parts). Next, the mixture is cooled to 180 ° C., 121 parts by weight (1.5 mol parts) of trimellitic anhydride is added, and after 2 hours of reaction under normal pressure sealing, the reaction is continued at 220 ° C. and normal pressure until the softening point is 180 ° C. A polyester resin (Mn = 8,500) was obtained.
Into a beaker, 20 parts by weight of copper phthalocyanine, 4 parts by weight of a colorant dispersant “Solsper's 28000” [manufactured by Avicia Co., Ltd.], 20 parts by weight of the obtained polyester resin and 56 parts by weight of ethyl acetate were added and stirred uniformly. After the dispersion, copper phthalocyanine was finely dispersed by a bead mill to obtain a colorant dispersion. The volume average particle diameter measured with “LA-920” of the colorant dispersion was 0.2 μm.

<Production Example 31> [Production of modified wax]
In a pressure-resistant reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer and a dropping cylinder, 454 parts by weight of xylene, low molecular weight polyethylene “Sunwax LEL-400” [softening point: 128 ° C., manufactured by Sanyo Chemical Industries, Ltd.] 150 parts by weight were added, and after nitrogen substitution, the temperature was raised to 170 ° C. with stirring. At the same temperature, 595 parts by weight of styrene, 255 parts by weight of methyl methacrylate, 34 parts by weight of di-t-butylperoxyhexahydroterephthalate, and xylene 119 A part by weight of the mixed solution was added dropwise over 3 hours, and the mixture was further maintained at the same temperature for 30 minutes. Subsequently, xylene was distilled off under a reduced pressure of 0.039 MPa to obtain a modified wax. The modified wax had a graft chain SP value of 10.35 (cal / cm ³ ) ^1/2 , Mn of 1,900, Mw of 5,200, and Tg of 56.9 ° C.

<Production Example 32> [Production of release agent dispersion]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling tube and a thermometer, 10 parts by weight of paraffin wax “HNP-9” [Ta: 73 ° C., manufactured by Nippon Seiki Co., Ltd.], obtained in Production Example 12 1 part by weight of the modified wax and 33 parts by weight of ethyl acetate were 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, and the paraffin wax was crystallized into fine particles. And then wet pulverized with Ultra Visco Mill (manufactured by IMEX) to obtain a release agent dispersion. The volume average particle diameter was 0.25 μm.

<Production Example 33> [Production of Resin Solution (D-1)]
In a reaction vessel equipped with a stirrer and a thermometer, 30 parts by weight of the colorant dispersion, 140 parts by weight of the release agent dispersion, 100 parts by weight of the toner binder (R-3) obtained in Example 3, and 153 ethyl acetate. A part by weight was added and stirred to uniformly dissolve the toner binder to obtain a resin solution (D-1).

<Production Examples 34 to 46> [Production of Resin Solutions (D-2) to (D-11), (D′-1) to (D′-3)]
In Production Example 33, 100 parts by weight of the toner binder (R-3) was changed to 100 parts by weight of the toner binders (R-4) to (R-13) and (R′-1) to (R′-3), respectively. Except having carried out, it carried out similarly to manufacture example 33, and obtained resin solution (D-2)-(D-11), (D'-1)-(D'-3).

  Table 4 shows the compositions of the resin solutions (D-1) to (D-11) and (D′-1) to (D′-3) obtained in Production Examples 33 to 46.

Example 14 [Production of Toner (S-1)]
100 parts by weight of toner binder (R-1), 8 parts by weight of carbon black “MA-100” (Mitsubishi Chemical Corporation), 5 parts by weight of carnauba wax, charge control agent “T-77” [manufactured by Hodogaya Chemical Co., Ltd. )] 1 part by weight was added, premixed using a Henschel mixer “FM10B” [Mitsui Miike Chemical Co., Ltd.], and then kneaded with a twin-screw kneader “PCM-30” [manufactured by Ikegai] . Then, after finely pulverizing using a supersonic jet pulverizer “Lab Jet” [manufactured by Nippon Pneumatic Industry Co., Ltd.], it is classified with an airflow classifier “MDS-I” [manufactured by Nippon Pneumatic Industry Co., Ltd.] Toner particles having a D50 of 8 μm were obtained. Next, 100 parts by weight of toner particles were mixed with 0.5 parts by weight of colloidal silica “Aerosil R972” [manufactured by Nippon Aerosil Co., Ltd.] using a sample mill to obtain toner (S-1) of the present invention.

Example 15 [Production of Toner (S-2)]
In Example 14, the toner (S-2) of the present invention is obtained in the same manner as in Example 14 except that 100 parts by weight of the toner binder (R-1) is changed to 100 parts by weight of the toner binder (R-2). It was.

Example 16 [Production of Toner (S-3)]
In a beaker, 170.2 parts by weight of ion-exchanged water, 0.3 part by weight of [Fine Particle Dispersion 1], 1 part by weight of sodium carboxymethyl cellulose, 48.5% by weight aqueous solution of “doleminol MON-7” sodium dodecyl diphenyl ether disulfonate Sanyo Chemical Industries Co., Ltd.] 36 parts by weight and 15.3 parts by weight of ethyl acetate were added and stirred to dissolve uniformly. Next, the temperature was raised to 50 ° C., and 75 parts by weight of the resin solution (D-1) was added and stirred for 2 minutes while stirring the TK auto homomixer at 10,000 rpm at the same temperature. Next, this mixed liquid was transferred to a reaction vessel equipped with a stirrer and a thermometer, and ethyl acetate was distilled off at 50 ° C. until the concentration became 0.5% by weight or less to obtain an aqueous resin dispersion of toner particles. Next, washing and filtration were performed, followed by drying at 40 ° C. for 18 hours to obtain toner particles with a volatile content of 0.5% by weight or less. Next, 10 parts by weight of toner particles were mixed with 0.05 part by weight of colloidal silica “Aerosil R972” [manufactured by Nippon Aerosil Co., Ltd.] using a sample mill to obtain toner (S-3) of the present invention.

<Examples 17 to 24, Comparative Examples 4 to 6> [Production of Toners (S-4) to (S-11) and (S′-1) to (S′-3)]
In Example 16, 75 parts by weight of the resin solution (D-1) is changed to 75 parts by weight of the resin solutions (D-2) to (D-9) and (D′-1) to (D′-3), respectively. Otherwise, toners (S-4) to (S-11) and (S′-1) to (S′-3) were obtained in the same manner as in Example 16.

<Example 25> [Production of toner (S-12)]
In a beaker, 108 parts by weight of decane and 2.1 parts by weight of [Fine Particle Dispersion 2] were added and stirred to dissolve uniformly. Next, the temperature was raised to 50 ° C., and 75 parts by weight of the resin solution (D-10) was added and stirred for 2 minutes while stirring the TK auto homomixer at 10,000 rpm at the same temperature. The mixture was then transferred to a reaction vessel equipped with a stirrer and a thermometer. Ethyl acetate was distilled off at 50 ° C. until the concentration reached 0.5% by weight or less, then washed, filtered, and 18 ° C. at 40 ° C. The toner particles were obtained by drying for a period of time and setting the volatile content to 0.5% by weight or less. Then, 0.05 part by weight of colloidal silica “Aerosil R972” [manufactured by Nippon Aerosil Co., Ltd.] was mixed with 10 parts by weight of the toner particles with a sample mill to obtain the toner (S-12) of the present invention.

<Example 26> [Production of toner (S-13)]
In Example 25, a toner (S-13) was obtained in the same manner as in Example 25 except that 75 parts by weight of the resin solution (D-10) was changed to 75 parts by weight of the resin solution (D-11).

  For the toners (S-1) to (S-13) and (S′-1) to (S′-3), the volume average particle diameter and particle size distribution are measured by the following methods, and the low temperature fixability and heat resistant storage stability are measured. And image strength were evaluated. The results are shown in Table 5.

[1] Volume average particle diameter, particle size distribution Toners (S-1) to (S-13) and (S′-1) to (S′-3) are dispersed in water, and a Coulter counter “Multisizer III” is used. D50 and particle size distribution were measured by (Beckman Coulter, Inc.).

[2] Heat-resistant storage stability Toners (S-1) to (S-13) and (S′-1) to (S′-3) are allowed to stand at 50 ° C. for 24 hours, and the degree of blocking is visually observed. The heat resistant storage stability was evaluated according to the following criteria.
[Evaluation criteria]
○: Blocking has not occurred.
X: Blocking has occurred.

[3] Low-temperature fixability The toners (S-1) to (S-13) and (S′-1) to (S′-3) are uniformly placed on the paper so as to be 0.6 mg / cm ² (this When the powder is placed on the paper surface, a printer from which the heat fixing machine is removed is used.Other methods may be used as long as the powder can be placed uniformly at the above-mentioned weight density). The cold offset generation temperature (MFT) was measured 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 10 kg / cm ² . The lower the temperature at which cold offset occurs, the better the low-temperature fixability.

[4] Image strength The image fixed in the evaluation of low temperature fixability is subjected to a scratch test by applying a load of 10 g from right above the pencil fixed at 45 degrees according to JIS K5600. Image intensity was evaluated. Higher pencil hardness means better image strength.

The toner binder of the present invention is excellent in low-temperature fixability and anti-blocking properties, and is excellent in image strength of toner and printed matter. It is useful as particles, base particles for electrophotographic toner, base particles for electrostatic recording toner, base particles for electrostatic printing toner, hot melt adhesive and the like.

Claims (8)

  A toner binder comprising a crystalline resin (A), wherein (A) has an ester group, and (A) has a maximum peak heat temperature (Ta) of 40 to 100 ° C. Toner binder having a pencil hardness of 4B to 5H.   The toner binder according to claim 1, wherein the crystalline resin (A) has a pencil hardness of 3B to 4H.   The toner binder according to claim 1 or 2, wherein the crystalline resin (A) has a heat of fusion of 20 to 90 J / g. The toner binder according to claim 1, wherein the crystalline resin (A) satisfies the following condition 1.
[Condition 1] 1 × 10 ³ ≦ G ′ (Ta + 20) ≦ 1 × 10 ⁶
[G ′ (Ta + 20): (A) storage elastic modulus (Pa) at (Ta + 20) ° C.]   The toner binder according to claim 1, wherein the crystalline resin (A) is a resin having a urethane group and a urea group.   6. The toner binder according to claim 5, wherein the urea group concentration of the crystalline resin (A) based on the weight of (A) is 0.1 to 5.0% by weight. The toner binder according to claim 5 or 6, wherein the crystalline resin (A) satisfies the following condition 2.
[Condition 2] 5.0 ≦ 1.17 × (A-urethane) + 2.13 × (A-urea) −2.23
[(A-urethane); (A) urethane group concentration (% by weight), (A-urea); (A) urea group concentration (% by weight)] A toner comprising the toner binder according to claim 1.