JP2017187748A - Toner binder and method for producing the same, and resin particle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner binder capable of satisfying three performances of low temperature fixability, hot off-set resistance and glossiness.SOLUTION: A toner binder contains a prepolymer (A) having an isocyanate group (d) and an amine compound (B) and/or polyurethane urea (C) formed by extension reaction with water, where the prepolymer (A) is a prepolymer obtained by reaction of diisocyanate (D1), tri- or higher polyisocyanate (D2) and polyol (E) as components, and a molar ratio (D1)/(D2) between diisocyanate (D1) and tri- or higher polyisocyanate (D2) is 1.0 to 40.0.SELECTED DRAWING: None

Description

  The present invention relates to a toner binder, a production method thereof, and resin particles.

  The toner binder for electrophotography, which is commonly used as an image fixing method in copying machines and printers, does not fuse the toner to the heat roll even at a high fixing temperature (hot offset resistance), fixing. There is a demand for fixing toner (low temperature fixability) even at low temperatures. Further, there is a great demand for higher image quality, and in particular, full-color copying machines and full-color printers are required to provide high-gloss images (high gloss).

A polyester-based toner binder is used to develop low-temperature fixability, and a toner binder that can improve low-temperature fixability by introducing crystalline polyester into the toner has been proposed (Patent Document 1). .
However, such a toner is likely to cause a problem (hot offset) that the toner is fused to the heat roll.

As means for solving such a problem, for example, a toner composed of a vinyl polymer that is appropriately crosslinked using a crosslinking agent and a molecular weight regulator (Patent Document 2), and a weight average molecular weight (Mw) and number A toner (Patent Document 3) having a broad molecular weight distribution so that the ratio Mw / Mn to the average molecular weight (Mn) is 3.5 to 40 has been proposed.
On the other hand, a toner (such as Patent Documents 4 to 12) using a urethane-modified polyester resin formed by reacting a polyester resin and a polyvalent isocyanate, or a polyester resin having a cross-link as a skeleton, and further at the terminal A toner using a modified polyester prepolymer having a reactive functional group (Patent Document 13) has also been proposed.

  However, each of these toners can achieve both low temperature fixability and hot offset resistance, or both low temperature fixability and glossiness, but it has three performances: low temperature fixability, hot offset resistance and glossiness. At the same time, I can't be satisfied.

JP 2002-287426 A Japanese Patent Publication No.51-2334 Japanese Patent Publication No.55-6805 JP-A 63-56659 Japanese Patent Laid-Open No. 1-154068 Japanese Patent Laid-Open No. 2-166464 JP-A-2-308175 JP-A-4-211272 JP 11-282203 A Japanese Patent Laid-Open No. 11-305481 JP 2000-234011 A JP 2004-258627 A JP 2008-233360 A

  An object of the present invention is to provide a toner binder having both low-temperature fixability and hot offset resistance and excellent gloss, a method for producing the toner binder, and resin particles containing the binder.

The inventors of the present invention have reached the present invention as a result of studies to achieve the above object.
That is, the present invention is a toner binder containing a polyurethane urea (C) formed by an extension reaction of a prepolymer (A) having an isocyanate group (d) with an amine compound (B) and / or water, The prepolymer (A) is a prepolymer obtained by reacting a diisocyanate (D1), a trivalent or higher polyisocyanate (D2), and a polyol (E) as constituent raw materials, and has a trivalent or higher polyisocyanate (D2). And a diisocyanate (D1) molar ratio (D1) / (D2) of 1.0 to 40.0 toner binder; resin particles containing the toner binder; isocyanate group-containing prepolymer Contains polyurethaneurea (C) formed by elongation reaction of (A) with amine compound (B) and / or water A method for producing a toner binder.

  The toner using the toner binder of the present invention has an effect that it is possible to simultaneously satisfy the three performances that are difficult to achieve at the same time: low-temperature fixability, hot offset resistance, and glossiness.

Hereinafter, the toner binder of the present invention will be described.
The toner binder of the present invention is a toner binder containing polyurethane urea (C) as an essential component, and this polyurethane urea (C) comprises a prepolymer (A) having an isocyanate group (d) and an amine compound (B). ) And / or an extension reaction with water. Further, this prepolymer (A) is a prepolymer obtained by reacting diisocyanate (D1), triisocyanate or higher polyisocyanate (D2) and polyol (E) as constituent raw materials, and further comprising diisocyanate (D1) and The trivalent or higher polyisocyanate (D2) and the molar ratio (D1) / (D2) are 1.0 to 40.0.

  The polyurethane urea (C), which is an essential component of the toner binder of the present invention, is an elongation reaction between the prepolymer (A) having an isocyanate group (d) and the amine compound (B), or the prepolymer (A) and water. It is formed by an extension reaction. The amine compound (B) and water may be used in combination.

  The prepolymer (A) having an isocyanate group (d) of the present invention can be obtained by reacting diisocyanate (D1), trivalent or higher polyisocyanate (D2) and polyol (E) as constituent raw materials.

  Examples of the diisocyanate (D1) used in the present invention include aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates.

  Examples of the aliphatic diisocyanate compound include trimethylene diisocyanate (TDI), tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2 4,4-trimethylhexamethylene diisocyanate and the like.

  Examples of the alicyclic diisocyanate compound include 1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate (IPDI), hydrogenated diphenylmethane diisocyanate (hydrogenated MDI), and hydrogen. Added xylylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated tetramethyl xylylene diisocyanate and the like.

  Examples of the aromatic diisocyanate compound include phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,2′-didiphenylmethane diisocyanate (MDI), 4,4′-diphenylmethane diisocyanate, 4 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate and the like.

  Among the diisocyanates (D1), preferred are aromatic diisocyanates having 6 to 15 carbon atoms, aliphatic diisocyanates having 4 to 12 carbon atoms, and alicyclic diisocyanates having 4 to 15 carbon atoms, and particularly preferred are TDI, MDI, HDI, hydrogenated MDI, and IPDI. Diisocyanate (D1) may be used alone or in combination.

  The polyisocyanate having 3 or more valences (D2) is not particularly limited as long as it is a compound having 3 to 8 isocyanate groups, but is a compound having a triisocyanate, tetraisocyanate, isocyanurate structure (D21), or a compound having a biuret structure. (D22), a compound containing an adduct structure (D23), and the like.

  Examples of the triisocyanate compound include a compound represented by the following general formula (1).

  Examples of the tetraisocyanate compound include compounds represented by the following general formula (2).

[Wherein R ₂ represents an alkylene group. ]

Examples of the compound (D21) having an isocyanurate structure include an isocyanurate trimer and an isocyanurate pentamer, and also an isocyanurate heptamer and a multimer more than a 9mer.
The isocyanurate trimer is a polyisocyanate composed of three molecules of a diisocyanate monomer and having an isocyanurate group, and examples thereof include compounds represented by the following general formula (3).

  [Wherein, R represents a residue obtained by removing one isocyanate group from a diisocyanate monomer. ]

  The isocyanurate pentamer is a polyisocyanate having an isocyanurate structure composed of five diisocyanate monomers, and examples thereof include compounds represented by the following general formula (4).

  [Wherein, -R represents a residue obtained by removing one isocyanate group from a diisocyanate monomer, and -R- represents a residue obtained by removing two isocyanate groups from a diisocyanate monomer. ]

  The compound (D22) having a biuret structure is formed from urea and an isocyanate group, and examples thereof include a compound represented by the following general formula (5).

  [Wherein, R represents a residue obtained by removing one isocyanate group from a diisocyanate monomer. ]

  Examples of the compound having an adduct structure (D23) include compounds represented by the following general formula (6).

[Wherein R ₁ represents an alkyl group, and R ₂ represents an alkylene group. ]

  Of the trivalent or higher polyisocyanates (D2), from the viewpoint of hot offset resistance and gloss, the polyisocyanate (D2) is preferably a trivalent to tetravalent polyisocyanate, and more preferably a compound (D21) having an isocyanurate structure. A compound (D22) having a biuret structure and a compound (D23) containing an adduct structure. Trivalent or higher polyisocyanate (D2) may be used alone or in combination.

The molar ratio (D1) / (D2) between the diisocyanate (D1) and the trivalent or higher polyisocyanate (D2) is 1.0 to 40.0, preferably 2.0 to 35.0, more preferably 5.0. ~ 30.0.
When (D1) / (D2) is less than 1, hot offset resistance may deteriorate, and when (D1) / D2) exceeds 40, glossiness may deteriorate.

The combination of the polyisocyanate (D2) having 3 or more valences and the diisocyanate (D1) is not limited, but preferred combinations from the viewpoint of glossiness include the following two.
(1) When the polyisocyanate (D2) having a valence of 3 or more is a polyisocyanate derived from an aromatic diisocyanate, the combination in which the isocyanate (D1) is an aliphatic diisocyanate and / or an alicyclic diisocyanate (2) A valence of 3 or more When the polyisocyanate (D2) is a polyisocyanate derived from an aliphatic diisocyanate, the combination in which the diisocyanate (D1) is an alicyclic diisocyanate

  Examples of the polyol (E) that is a constituent material of the prepolymer (A) include a diol (e1) and a tri- to octavalent or higher polyol (e2).

Examples of the diol (e1) 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, tetradecandiol, neopentyl glycol and 2,2-diethyl-1,3-propanediol);
Number average molecular weight (hereinafter sometimes abbreviated as Mn) = 106 to 20,000 alkylene ether glycol (for example, diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol) ;
An alicyclic diol having 6 to 24 carbon atoms (for example, 1,4-cyclohexanedimethanol and hydrogenated bisphenol A);
Mn = 100 to 10,000 alkylene oxide of the alicyclic diol (hereinafter, “alkylene oxide” may be abbreviated as AO) adduct (addition mole number 2 to 100) [for example, 1,4-cyclohexane Ethylene oxide of dimethanol (hereinafter, “ethylene oxide” may be abbreviated as EO) 10 mol adduct, etc.]; bisphenols having 13 to 30 carbon atoms (bisphenol A, bisphenol F, bisphenol S, etc.) or carbon AO [EO, propylene oxide (hereinafter, “propylene oxide” may be abbreviated as PO) and butylene oxide, etc.) and adducts (addition mole number) of polyphenols of 12 to 24 (for example, catechol, hydroquinone, resorcin, etc.) 2 to 100) (for example, bisphenol A · EO) To 4 mol adduct and bisphenol A · PO2~4 mole adduct);
Weight average molecular weight (hereinafter sometimes abbreviated as Mw) = 100-5,000 polylactone diol (for example, poly-ε-caprolactone diol, etc.);
A polybutadiene diol of Mw = 1,000-20,000;
Polyester diols having Mw = 800 to 150,000; and polycarbonates, polyisoprene polyols and hydrogenated polyisoprene polyols having Mw = 800 to 50,000.

As the polyol (e2) having 3 to 8 or more valences, an aliphatic polyhydric alcohol having 3 to 8 or more valences having 3 to 10 carbon atoms (for example, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitan). And AO (2 to 4 carbon atoms) adduct (addition mole number 2 to 100) of trisphenol having 25 to 50 carbon atoms (for example, trisphenol · EO 2 to 4 mol adduct and trisphenol PA · PO 2 −). 4 mol adducts, etc.); AO (carbon number 2-4) adducts (addition mol number 2-100) (phenol novolac PO 2 mol adducts) of 3 to 50 novolak resins (for example, phenol novolak and cresol novolak). And phenol novolac EO 4 mol adduct); polyphenols having 6 to 30 carbon atoms (examples) Pyrogallol, phloroglucinol and 1,2,4-benzenetriol, etc.) AO (2 to 4 carbon atoms) adduct (2 to 100 mol added) (pyrogallol EO 4 mol adduct); Mw = 800 to 150, 000 polyester polyols; and acrylic polyols having a polymerization degree of 20 to 2,000 {monomers having hydroxyethyl (meth) acrylate and other polymerizable double bonds [for example, styrene, (meth) acrylic acid and (meth) acrylic] Acid ester etc.] and the like.
Of these, an AO adduct of an aliphatic polyhydric alcohol and a novolac resin is preferred, and an AO adduct of a novolak resin is more preferred.

  Among the polyols (E), the diol (e1) is preferable, and more preferable is an alkylene ether glycol having Mn = 106 to 20,000, an AO adduct of bisphenols having 13 to 30 carbon atoms, a polyester polyol (E1). Particularly preferred is polyester diol (E11).

  Here, the polyester polyol (E1) is a polyol having two or more hydroxyl groups at the terminals in a polyester obtained by polycondensation of the polyol component (x) and the polycarboxylic acid component (y). Examples of the polyester polyol (E1) include a polyester diol (E11) having two hydroxyl groups at the terminal and a polyester polyol (E12) having three or more hydroxyl groups at the terminal. Of these, polyester diol (E11) having two hydroxyl groups at the terminal is preferable from the viewpoint of gloss.

  As the polyol component (x) which is a constituent raw material of the polyester polyol (E1), those exemplified for the diol (e1) and the tri- to octa- or higher-valent polyol (e2) can be used, which is preferable from the viewpoint of gloss. Is a diol (e1).

As the polycarboxylic acid component (y) which is a constituent raw material of the polyester polyol (E1), dicarboxylic acid (y1) and trivalent to hexavalent or higher polycarboxylic acid (y2) can be used.
Examples of the dicarboxylic acid (y1) include alkane dicarboxylic acids having 4 to 32 carbon atoms (such as succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, and octadecanedicarboxylic acid); alkene dicarboxylic acids having 4 to 32 carbon atoms. (Eg, maleic acid, fumaric acid, citraconic acid, mesaconic acid, etc.); branched alkene dicarboxylic acids having 8 to 40 carbon atoms [eg, dimer acid, alkenyl succinic acid (dodecenyl succinic acid, pentadecenyl succinic acid, and octadecenyl succinic acid) Branched alkane dicarboxylic acids having 12 to 40 carbon atoms [eg alkyl succinic acid (decyl succinic acid, dodecyl succinic acid and octadecyl succinic acid etc.); aromatic dicarboxylic acids having 8 to 20 carbon atoms (eg phthalic acid, isophthalic acid, etc.) , Terephthalic acid and naphthalenedicarboxylic acid, etc. Etc. The.

Examples of the tri- or hexavalent polycarboxylic acid (y2) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (for example, trimellitic acid and pyromellitic acid), and aliphatic groups having 6 to 36 carbon atoms ( And polycarboxylic acids (including alicyclic) such as hexanetricarboxylic acid and decanetricarboxylic acid.
Of these polycarboxylic acid components (y), dicarboxylic acid (y1) is preferable from the viewpoint of gloss.

  As a constituent material of the polyester polyol (E1), monools and monocarboxylic acids can be used as long as the performance of the toner binder is not affected.

Of the isocyanate groups (d) in the prepolymer (A), the content (% by weight) of the isocyanate groups (d1) derived from the diisocyanate (D1) based on the weight of the prepolymer (A) and the polyisocyanate (D2) It is preferable from the viewpoint of hot offset resistance and gloss that the content (% by weight) of the isocyanate group (d2) derived from the above satisfies the following relational expression (2).
0.6 ≦ d1 / (d1 + d2) ≦ 1.0 (2)

  The value of d1 / (d1 + d2) is more preferably 0.8 to 1.0, and still more preferably 0.95 to 1.0.

  The urethane group concentration in the prepolymer (A) is preferably 1.0 to 8.0% by weight, more preferably 1 based on the weight of the prepolymer (A) from the viewpoint of hot offset resistance and gloss. It is 0.5 to 7.5% by weight, and more preferably 2.0 to 7.0% by weight.

  Examples of the amine compound (B) of the present invention include a bifunctional or higher amine compound (B1) and an amine compound (B2) obtained by blocking (B1).

Examples of the bifunctional or higher amine (B1) include aliphatic diamines having 2 to 18 carbon atoms (B11) and aromatic diamines having 6 to 20 carbon atoms (B12).
Examples of the aliphatic diamine (B11) having 2 to 18 carbon atoms include a chain aliphatic diamine (B111) and a cyclic aliphatic diamine (B112).

Examples of the chain aliphatic diamine (B111) include alkylene diamines having 2 to 12 carbon atoms (ethylene diamine, propylene diamine, trimethylene diamine, tetramethylene diamine, hexamethylene diamine, etc.) and polyalkylene (2 to 6 carbon atoms) polyamine [ Diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and the like.
Cycloaliphatic diamines (B112) 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 etc.} and a heterocyclic diamine having 4 to 15 carbon atoms [piperazine, N-amino Ethylpiperazine, 1,4-diaminoethylpiperazine, 1,4-bis (2-amino-2-methylpropyl) piperazine, etc.].

  Examples of the aromatic diamine having 6 to 20 carbon atoms (B12) include an unsubstituted aromatic diamine and 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). And aromatic 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.

The amine compound that undergoes elongation reaction with the prepolymer (A) may be a blocked amine compound (B2). This is because if the block is removed, it acts as an amine compound (B1).
Examples of such blocked amine compound (B2) include ketimine compounds and oxazolidine obtained by reacting the bifunctional or higher amine (B1) with ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Compounds and the like.

  Among the amine compounds (B), 4,4'-diaminodiphenylmethane, xylylenediamine, isophoronediamine, ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine and mixtures thereof are preferable.

  In order to cause the prepolymer (A) to undergo an elongation reaction, water may be used instead of the amine compound (B), or the amine compound (B) and water may be used in combination. However, from the viewpoint of reactivity, when water is used alone, the reactivity with the prepolymer (A) is inferior to that of the amine compound (B), so it is necessary to carry out the reaction at 40 to 50 ° C. for 24 hours or more. There is a case.

  As a mixing ratio of the amine compound (B) and / or water to the prepolymer (A) having an isocyanate group (d), the isocyanate group and the amine compound (B in the prepolymer (A) having an isocyanate group (d) are used. ) When the equivalent ratio with active hydrogen in the medium and / or water is [NCO] / [H], it is preferably 1 / 2-2 / 1, more preferably 1.5 / 1 from the viewpoint of hot offset resistance. ˜1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2. In addition, when extending | stretching reaction with water, water is handled as a bivalent active hydrogen containing compound.

The Mw of the prepolymer (A) having an isocyanate group (d) is usually 10,000 to 300,000, preferably 15,000 to 250,000, more preferably 20 from the viewpoint of hot offset resistance and gloss. , 000-200,000.
In this invention, Mn and Mw of resin, such as a prepolymer (A), can be measured on condition of the following using GPC.

Device (example): HLC-8120 manufactured by Tosoh Corporation
Column (example): TSK GEL GMH6 2 [Tosoh Corp.]
Measurement temperature: 40 ° C
Sample solution: 0.25 wt% THF solution Solution injection amount: 100 μl
Detection device: Refractive index detector Reference material: Tosoh Co., Ltd. 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)
The molecular weight is measured by dissolving a polyester resin or the like in THF and filtering out the insoluble matter with a glass filter.

Furthermore, the weight average molecular weight of the prepolymer (A) (Mw) to number average molecular weight of the molecular weight distribution obtained by dividing the _(Mn) (W A), the difference between the molecular weight distribution of the polyol _(E) (W E) The toner binder of the present invention preferably satisfies the following relational expression (1).
1.5 ≦ W _A −W _E ≦ 5.0 (1)

Here, _{W A} is the weight average molecular weight of the prepolymer (A) _(Mw A) / number is calculated by the average molecular weight (Mn _A), the weight average molecular weight of _{W E} is polyol (E) _(Mw E) / number average molecular weight Calculated as (Mn _E ).

The value of W _A -W _E is preferably 1.8 ≦ W _A −W _E ≦ 4.0, more preferably 2.0 ≦ W _A −W _E ≦ 3, from the viewpoint of hot offset resistance and glossiness. .5.

An amorphous polyester resin (L) that does not react with any of the prepolymer (A) having an isocyanate group (d) and the amine compound (B) can also be used in combination.
By using this non-crystalline polyester resin (L) in combination, the low-temperature fixability and glossiness are improved, and the polyurethane formed by subjecting the isocyanate group-containing prepolymer (A) to an amine compound and / or water by an extension reaction. It is preferable to use urea (C) alone.

  The “non-crystalline” of the non-crystalline polyester resin (L) means a softening temperature measured by a Kaohashi flow tester and a maximum peak temperature of heat of fusion measured by a differential scanning calorimeter (DSC). A resin having a ratio of [melting point] [softening temperature / maximum peak temperature of melting heat (melting point)] greater than 1.55 and having a property of being softly softened by heat is referred to as “non-crystalline resin”.

  In addition to the polyurethane urea (C) and the amorphous polyester resin (L), it is preferable to further contain a crystalline resin (M) from the viewpoint of low-temperature fixability.

  In the present invention, “crystallinity” refers to a resin having a property that the ratio of softening temperature / maximum peak temperature of heat of fusion is 0.80 to 1.55 and softens sharply by heat. And

The content of the polyurethane urea (C) of the present invention is the amount of the polyurethane urea (C) based on the weight of the toner binder. The amount of polyurethane urea (C) is the total amount of prepolymer (A) and amine compound (B). The amount of the toner binder is a total amount of polyurethane urea (C), an amorphous resin (L) described later, and a crystalline resin (M).
The content of the polyurethane urea (C) is preferably 0.1 to 50.0% by weight, more preferably 3.0 to 40.0, based on the weight of the toner binder, from the viewpoint of hot offset resistance and gloss. % By weight, more preferably 5.0 to 30.0% by weight.

  “Crystallinity” of the crystalline resin in the present invention is the ratio between the softening temperature measured by the Koka flow tester and the maximum peak temperature (melting point) of the heat of fusion measured by a differential scanning calorimeter (DSC). (Softening temperature / Maximum peak temperature of melting heat (melting point)) is preferably 0.80 to 1.55, and is a property of being softened sharply by heat. A resin having this property is referred to as “crystalline resin”. To do.

  The crystalline structure of the crystalline resin (M) is not particularly limited as long as it is compatible with the polyurethane urea (C) and the amorphous resin (L). Examples thereof include compounds such as crystalline polyester, crystalline polyurethane, crystalline polyurea, crystalline polyamide, and crystalline polyvinyl. Among these, crystalline polyester is preferable from the viewpoint of compatibility. From the viewpoint of crystallinity, a crystalline polyester resin in which the linear aliphatic diol content of the diol component is 80 mol% or more is preferable.

The resin particles of the present invention are resin particles containing a toner binder, and are resin particles used in an electrophotographic apparatus that employs a heat fixing method as a fixing method.
In addition to the toner binder of the present invention, the resin particles 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, pigments and the like used as 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.

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 and the like), fatty acids having 30 to 50 carbon atoms (e.g., triacontanecarboxylic acid and the like), 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 rate of each component which comprises the resin particle of this 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 resin particles from the viewpoint of low-temperature fixability.
When a colorant is used, the content of the colorant is preferably 0.001 to 60% by weight, more preferably 0.1 to 55% by weight, and particularly preferably 0.1 to 55% by weight based on the weight of the resin particles from the viewpoint of gloss. Preferably it is 0.5 to 50 weight%.
When a release agent is used, the content of the release agent is preferably 0.001 to 30% by weight, more preferably 0.5 to 20% by weight, based on the weight of the resin particles from the viewpoint of gloss. Particularly preferably, it is 1 to 10% by weight.
When using a charge control agent, the content of the charge control agent is preferably 0.001 to 20% by weight, more preferably 0.1 to 10% by weight based on the weight of the resin particles from the viewpoint of low-temperature fixability. %, Particularly preferably 0.5 to 7.5% by weight.
When using a fluidizing agent, the content of the fluidizing agent is preferably 0.001 to 10% by weight, more preferably 0 to 5% by weight, based on the weight of the resin particles from the viewpoint of low temperature fixability. Particularly preferred is 0.1 to 4% by weight.

  The resin particles of the present invention are 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 an electric 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 resin particles 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 resin particles of the present invention can be measured using a Coulter counter “Multisizer III” (manufactured by Beckman Coulter, Inc.).

There is no restriction | limiting in particular about the manufacturing method of the resin particle of this invention, The thing obtained by the well-known kneading | pulverization grinding | pulverization method, the emulsion phase inversion method, the polymerization method, etc. may be used.
For example, when resin particles are obtained by a kneading pulverization method, the components constituting the resin particles excluding the fluidizing agent are dry blended, then melt kneaded, then coarsely pulverized, and finally finely pulverized using a jet mill pulverizer or the like. And then further classified to form fine particles having a volume average particle diameter of preferably 1 to 15 μm, and then mixed with a fluidizing agent. When the toner is obtained by the emulsion phase inversion method, the components constituting the toner excluding the fluidizing agent are dissolved or dispersed in an organic solvent, and then emulsified by adding water, etc., and then separated and classified. . Further, it may be produced by a method using organic fine particles described in JP-A No. 2002-284881 or a method of dispersing in carbon dioxide in a supercritical state described in JP-A No. 2007-277511.

Next, a method for producing the toner binder of the present invention will be described.
The method for producing the toner binder of the present invention can be broadly classified as follows.
(I) In order to obtain an isocyanate group-containing prepolymer (A), a reaction mixture of a polyol (E) and a polyisocyanate (D2) having a valence of 3 or more is reacted with a diisocyanate (D1). A manufacturing method of
(II) There is a batch preparation method in which the polyol (E), the trivalent or higher polyisocyanate (D2) and the diisocyanate (D1) are reacted.

  The manufacturing method of sequential charging of (I) is a manufacturing method of a toner binder containing polyurethane urea (C) formed by an extension reaction of an isocyanate group-containing prepolymer (A) with an amine compound (B) and / or water. In the method, the polyol (E) is first reacted with a polyisocyanate (D2) having a valence of 3 or more and then reacted with the diisocyanate (D1) to obtain an isocyanate group-containing prepolymer (A).

  On the other hand, the batch-prepared manufacturing method of (II) is a toner binder containing a polyurethane urea (C) formed by an extension reaction of an isocyanate group-containing prepolymer (A) with an amine compound (B) and / or water. In the production method, a polyol (E), a trivalent or higher polyisocyanate (D2), and a diisocyanate (D1) are reacted in order to obtain an isocyanate group-containing prepolymer (A).

In that case, considering the difference in reactivity between the polyisocyanate (D2) and the diisocyanate (D1) with respect to the polyol (E), the following conditions (1) or (D2) of the conditions (2) It is preferable to use in combination.
(1) When the polyisocyanate (D2) having three or more valences is a polyisocyanate derived from an aromatic diisocyanate, the isocyanate (D1) uses an aliphatic diisocyanate and / or an alicyclic diisocyanate.
(2) When the trivalent or higher polyisocyanate (D2) is a polyisocyanate derived from an aliphatic diisocyanate, the diisocyanate (D1) uses an alicyclic diisocyanate.

  The trivalent or higher polyisocyanate (D2) is derived from at least one diisocyanate selected from the group consisting of 2,4- and 2,6-tolylene diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate. It is preferable that the diisocyanate (D1) is at least one diisocyanate selected from the group consisting of isophorone diisocyanate, 4,4-dicyclohexylmethane diisocyanate, and hexamethylene diisocyanate.

  The method for producing a toner binder including the sequential reaction of (I) and the batch reaction of (II) makes the distance between the crosslinking points of the polyurethaneurea (C) constant, and the low-temperature fixability of the resin particles containing the toner binder. And hot offset resistance, and is excellent in glossiness.

  EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto.

Production Example 1 <Synthesis of Polyol (E-1)>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 439 parts by weight (60.6 mole parts) of bisphenol A · PO2 mole adduct, 329 parts by weight of bisphenol A · PO3 mole adduct (39.4 moles) Part), 206 parts by weight of terephthalic acid (66.8 parts by mole), 90 parts by weight of adipic acid (33.2 parts by mole) and 0.5 parts by weight of titanium diisopropoxybistriethanolamate as the condensation catalyst. The reaction was allowed to proceed for 10 hours under a reduced pressure of 0.5 to 2.5 kPa while gradually raising the temperature to 0C. When the acid value became less than 1, it was taken out to obtain a polyol (E-1).
Polyol (E-1) had a Tg of 45 ° C., a hydroxyl value of 25, a number average molecular weight of 3,900, a weight average molecular weight of 11,000, and a molecular weight distribution of 2.8.

Production Examples 2 to 4 <Synthesis of Polyols (E-2) to (E-4)>
A polyhydric alcohol and a polycarboxylic acid described in Table 1 were charged into a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and the reaction was conducted in the same manner as in Production Example 1 except that polyol (E-2 ) To (E-4) were obtained.

Production Example 5 <Synthesis of Polyol (E-5)>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 508 parts by weight (100 mole parts) of 3-methyl-1,5-pentanediol, 338 parts by weight of terephthalic acid (49.9 mole parts), adipine Acid 298 parts (50.1 mol parts) and titanium diisopropoxybistriethanolamate 0.5 parts by weight as a condensation catalyst were added, then the temperature was gradually raised to 220 ° C., and the product was produced at 220 ° C. under a nitrogen stream. The reaction was carried out for 4 hours while distilling off the water. Furthermore, it was made to react under the reduced pressure of 0.5-2.5 kPa for 10 hours. When the acid value became less than 1, it was taken out to obtain a polyol (E-5).
Polyol (E-5) had a Tg of −40 ° C., a hydroxyl value of 25, a number average molecular weight of 3,800, a weight average molecular weight of 11,000, and a molecular weight distribution of 2.9.

Production Example 6 <Synthesis of Polyol (E-6)>
A polyhydric alcohol and a polycarboxylic acid described in Table 1 were charged into a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and the reaction was carried out in the same manner as in Production Example 1 except that polyol (E-6 )

Production Example 7 <Synthesis of Polyol (E-7)>
Into a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, the polyhydric alcohol and polycarboxylic acid described in Table 1 were charged, and the reaction was conducted in the same manner as in Production Example 5 except that polyol (E-7 )

Production Example 8 <Polyol (E-8) Synthesis Polyhydric alcohol and polycarboxylic acid described in Table 1 were charged into a reaction vessel equipped with a condenser tube, a stirrer, and a nitrogen introduction tube, and the other production examples 1 In the same manner as above, a polyol (E-8) was obtained.

  Table 1 shows the compositions and physical properties of the polyols (E-1) to (E-8) obtained in Production Examples 1 to 8.

Production Example 9 <Synthesis of Prepolymer (A-1) Solution>
In a pressure-resistant reaction vessel equipped with a stirrer, a heating / cooling device and a thermometer, 452 parts by weight of polyol (E-1), Duranate TPA-100 (hexamethylene diisocyanate isocyanurate trimer; manufactured by Asahi Kasei Chemicals) (D21-1) ) 9 parts by weight and 500 parts by weight of ethyl acetate were added and reacted in a sealed state at 80 ° C. for 6 hours. Furthermore, 38 parts by weight of isophorone diisocyanate (IPDI) (D1-1) was added and reacted in a sealed state at 80 ° C. for 10 hours to obtain a prepolymer (A-1) solution containing an isocyanate group at the molecular end. .
The urethane group concentration of the prepolymer (A-1) was 2.6, the number average molecular weight was 5,600, the weight average molecular weight was 35,000, and the molecular weight distribution was 6.2.

Production Examples 2 to 8 <Prepolymer (A-2) Solution to (A-8) Solution Synthesis>
The polyol (E), trivalent or higher polyisocyanate (D2) and ethyl acetate described in Table 2 were reacted in the same manner as in Production Example 9 in a pressure-resistant reaction vessel equipped with a stirrer, a heating / cooling device and a thermometer. Furthermore, the diisocyanate (D1) described in Table 2 was added and reacted in the same manner as in Production Example 9 to obtain prepolymer (A-2) solution to (A-9) solution containing isocyanate at the molecular end. .

Production Example 17 <Synthesis of Prepolymer (A-9) Solution>
In a pressure-resistant reaction vessel equipped with a stirrer, a heating / cooling device and a thermometer, 452 parts by weight of polyol (E-1), 9 parts by weight of Duranate TPA-100 (D21-1), isophorone diisocyanate (IPDI) (D1-1) 38 Part by weight and 500 parts by weight of ethyl acetate were added and reacted in a sealed state at 80 ° C. for 10 hours to obtain a prepolymer (A-9) solution containing an isocyanate group at the molecular end.
The urethane group concentration of the prepolymer (A-9) was 2.6, the number average molecular weight was 5,500, the weight average molecular weight was 30,000, and the molecular weight distribution was 5.5.

Production Examples 18 to 21 <Synthesis of Prepolymer (A-10) Solution to (A-13) Solution>
The polyol (E), trivalent or higher polyisocyanate (D2) and ethyl acetate described in Table 2 were reacted in the same manner as in Production Example 9 in a pressure-resistant reaction vessel equipped with a stirrer, a heating / cooling device and a thermometer. Furthermore, the diisocyanate (D1) described in Table 2 was added and reacted in the same manner as in Production Example 9 to obtain a prepolymer (A-10) solution to an (A-13) solution containing isocyanate at the molecular end. .

Production Example 22 <Synthesis of Prepolymer (A-14) Solution>
Manufacture except using polyol (E), trivalent or higher polyisocyanate (D2), diisocyanate (D1), and ethyl acetate listed in Table 2 in a pressure-resistant reaction vessel equipped with a stirrer, heating / cooling device and thermometer. The reaction was conducted in the same manner as in Example 17 to obtain a prepolymer (A-14) solution containing an isocyanate at the molecular end.

Production Example 23 <Synthesis of Prepolymer (A-15) Solution>
Manufacture except using polyol (E), trivalent or higher polyisocyanate (D2), diisocyanate (D1), and ethyl acetate listed in Table 2 in a pressure-resistant reaction vessel equipped with a stirrer, heating / cooling device and thermometer. The reaction was conducted in the same manner as in Example 17 to obtain a prepolymer (A-15) solution containing an isocyanate at the molecular end.

Comparative Production Example 1 <Synthesis of Prepolymer (A′-1) Solution>
A pressure-resistant reaction vessel equipped with a stirrer, a heating / cooling device, and a thermometer was charged with 455 parts by weight of polyol (E-1), 45 parts by weight of isophorone diisocyanate (D1-1), and 500 parts by weight of ethyl acetate. The reaction was carried out at 10 ° C. for 10 hours to obtain a prepolymer (A′-1) solution containing an isocyanate group at the molecular end.
The urethane group concentration of the prepolymer (A′-1) was 2.4, the number average molecular weight was 6,900, the weight average molecular weight was 25,000, and the molecular weight distribution was 3.6.

Comparative Production Examples 2 to 5 <Synthesis of Prepolymer (A′-2) to (A′-5) Solution>
The reaction is performed in the same manner as in Comparative Example 1 except that the polyol resin, diisocyanate, and ethyl acetate listed in Table 2 are used in a pressure-resistant reaction vessel equipped with a stirrer, a heating / cooling device, and a thermometer. Prepolymers (A′-2) to (A′-5) were obtained.

Comparative Production Example 6 <Prepolymer (A′-6) Solution Synthesis>
500 parts by weight of polyol resin (E-8) and 500 parts by weight of ethyl acetate are put into a pressure-resistant reaction vessel equipped with a stirrer, a heating / cooling device and a thermometer, and stirred at 80 ° C. for 5 hours in a sealed state. A prepolymer (A′-6) solution containing no isocyanate group was obtained.

  About the prepolymer (A-1)-(A-14) solution obtained by manufacture example 1-14 and comparative manufacture example 1-6, (A'-1)-(A'-6) solution, each composition Table 2 shows the physical property values.

  In Table 2, (D1-2) is hexamethylene diisocyanate (HDI), (D22-1) is Duranate 24A-100 (HDI biuret; manufactured by Asahi Kasei Chemicals), and (D21-2) is VESTANT T1890 / 100. (IPDI isocyanurate trimer; manufactured by Evonik), (D23-1) is Duranate P301-75E (HDI adduct; manufactured by Asahi Kasei Chemicals), (D22-2) is a TDI trimer (TDI biuret) is there.

Production Example 24 <Synthesis of Amorphous Polyester Resin (L-1)>
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction tube, 418 parts by weight (58.5 parts by mole) of bisphenol A · PO2 mole adduct, 314 parts by weight (38.0 moles) of bisphenol A · PO3 mole adduct. Part), 10 parts by weight (3.5 parts by mole) trimethylolpropane, 243 parts by weight (82.3 parts by mole) terephthalic acid, 46 parts by weight (17.7 parts by mole) adipic acid, and titanium diisopropoxy as a condensation catalyst Next, 0.5 part by weight of bistriethanolamate was added, and the mixture was reacted for 10 hours under reduced pressure of 0.5 to 2.5 kPa while gradually raising the temperature to 230 ° C. Subsequently, it cooled to 180 degreeC, 31 parts of trimellitic anhydride was added, and it took out after reaction for 1 hour under normal pressure sealing, and obtained amorphous polyester resin (L-1).
The amorphous polyester resin (L-1) had a Tg of 58 ° C., a hydroxyl value of 28, an acid value of 18, a number average molecular weight of 3,000, and a weight average molecular weight of 9,500.

Production Example 25 <Synthesis of Crystalline Polyester Resin (M-1)>
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling pipe and a nitrogen introduction pipe, 387 parts by weight of 1,6-hexanediol (95.6 moles), 48 parts by weight of behenyl alcohol (4.4 moles) ), 687 parts by weight (100.0 parts by mole) of sebacic acid and 2.5 parts by weight of titanium diisopropoxybistriethanolamate as a polymerization catalyst, heated to 180 ° C., and produced at the same temperature under a nitrogen stream. The reaction is carried out for 10 hours while distilling off water, and then the reaction is carried out for 4 hours while distilling off the water produced under a nitrogen stream while gradually raising the temperature to 220 ° C., and further under reduced pressure of 0.007 to 0.026 MPa. The reaction was carried out while distilling off water, and when the acid value became 0.5 or less, it was taken out to obtain a crystalline polyester resin (M-1).
The crystalline polyester resin (M-1) had a Tm of 70 ° C., a hydroxyl value of 7, an acid value of 2, a number average molecular weight of 6,300, and a weight average molecular weight of 19,900.

Production Example 26 <Production of [fine particle dispersion]>
In a reaction vessel equipped with a stirrer, heating / cooling device, thermometer, cooling tube and nitrogen introduction tube, 690.0 parts by weight of water, sodium salt of polyoxyethylene monomethacrylate sulfate “Eleminol RS-30” [Sanyo Chemical Industries 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. And stirring for 15 minutes, a white emulsion was obtained.
Next, the temperature was raised to 75 ° C., and the reaction was performed 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 vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). [Fine particle dispersion] was obtained.
The volume average particle size of the particles dispersed in the fine particle dispersion was measured using a laser diffraction / scattering particle size distribution measuring apparatus “LA-920” (manufactured by Horiba, Ltd.). there were.
A part of [fine particle dispersion] was taken out and Tg and Mw were measured. As a result, Tg was 65 ° C. and Mw was 150,000.

Production Example 27 <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 by “LA-920” in [Colorant dispersion] was 0.2 μm.

Production Example 28 <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 “Sun Wax 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. Next, xylene was distilled off under reduced pressure of 0.039 MPa to obtain [modified wax].
The SP value of the graft chain of [modified wax] was 10.35 (cal / cm ³ ) ^1/2 , Mn was 1,900, Mw was 5,200, and Tg was 56.9 ° C.

Production Example 29 <Production of [Releasing Agent Dispersion]>
In a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling tube and a thermometer, paraffin wax “HNP-9” [Maximum heat of fusion peak temperature: 73 ° C., manufactured by Nippon Seiki Co., Ltd.] 10 parts by weight, production example 13 parts by weight of [modified wax] obtained in 13 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 paraffin The wax was crystallized into fine particles, and wet-pulverized with Ultraviscomyl (manufactured by Imex) to obtain a [release agent dispersion]. The volume average particle diameter was 0.25 μm.

Production Example 30 <Production of [Crystalline Polyester Resin (M-1) Dispersion]>
Into a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling tube and a thermometer, 20 parts by weight of crystalline polyester resin (M-1) and 80 parts by weight of ethyl acetate were added, and the temperature was raised to 78 ° C. with stirring. The mixture is stirred at the same temperature for 30 minutes, cooled to 30 ° C. over 1 hour to crystallize the crystalline polyester resin into fine particles, and further wet-pulverized with Ultraviscomyl (manufactured by IMEX), [Crystalline polyester resin (M -1) Dispersion] was obtained. The volume average particle size was 0.3 μm.

Production Example 31 <Production of blocked amine compound (B-3)>
Into a reaction vessel equipped with a stirrer, heating / cooling device, cooling pipe and thermometer, 50 parts by weight of isophorone diamine and 300 parts by weight of methyl ethyl ketone were added, reacted at 50 ° C. for 5 hours, then desolvated and blocked. An amine compound (B-3) was obtained.
The total amine value of the amine compound (B-3) was 415.

Example 1 <Production of Resin Particles (S-1)>
In a beaker, 170 parts by weight of ion-exchanged water, 0.3 parts by weight of [fine particle dispersion], 1 part by weight of sodium carboxymethyl cellulose, 48.5% by weight aqueous solution of “doleminyl MON-7”, “ELEMINOL MON-7” [Sanyo Chemical Industries Co., Ltd.] 36 parts by weight and 15 parts by weight of ethyl acetate were added and stirred to dissolve uniformly.
Next, 71 parts by weight of an amorphous polyester resin (L-1), 40 parts by weight of [colorant dispersion], 39 parts by weight of [release agent dispersion] and 54 parts by weight of ethyl acetate are added, and the toner is stirred. 18 parts by weight of the prepolymer (A-1) solution and 0.17 parts by weight of isophoronediamine (B-1) are added to the resin solution in which the binder is uniformly dissolved, and 2 times at 10,000 rpm with a TK auto homomixer. Stir for minutes. Next, this mixed solution 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 resin particles. Subsequently, the product was washed, filtered, and dried at 40 ° C. for 18 hours to adjust the volatile content to 0.5% by weight or less. Next, 1.0 part of colloidal silica (“Aerosil R972” manufactured by Nippon Aerosil Co., Ltd.) as an external additive was mixed with 100 parts of the toner particles by a sample mill to obtain the resin particles (S-1) of the present invention.

Example 2 <Production of Resin Particles (S-2)>
In Example 1, except that the prepolymer (A-1) solution is changed to a prepolymer (A-2) solution, and 0.17 parts by weight of isophoronediamine (B-1) is changed to 0.1 parts by weight. Resin particles (S-2) were obtained in the same manner as in Example 1.

Example 3 <Production of Resin Particles (S-3)>
Example 1 except that the prepolymer (A-1) solution is changed to a prepolymer (A-3) solution and 0.17 parts by weight of isophoronediamine (B-1) is changed to 0.12 parts by weight in Example 1. In the same manner as above, resin particles (S-3) were obtained.

Example 4 <Production of Resin Particles (S-4)>
Example 1 is the same as Example 1 except that the prepolymer (A-1) solution is changed to prepolymer (A-4) and 0.17 parts by weight of isophoronediamine (B-1) is changed to 0.52 parts by weight. Similarly, resin particles (S-4) were obtained.

Example 5 <Production of Resin Particles (S-5)>
In Example 1, resin particles (S-5) were obtained in the same manner as in Example 1 except that the prepolymer (A-1) solution was changed to the prepolymer (A-5) solution.

Example 6 <Production of Resin Particles (S-6)>
In Example 1, resin particles (S-6) were obtained in the same manner as in Example 1 except that the prepolymer (A-1) solution was changed to the prepolymer (A-6) solution.

Example 7 <Production of Resin Particles (S-7)>
In Example 1, resin particles (S-7) were obtained in the same manner as in Example 1 except that the prepolymer (A-1) solution was changed to the prepolymer (A-7) solution.

Example 8 <Production of Resin Particles (S-8)>
In Example 1, resin particles (S-8) were obtained in the same manner as in Example 1 except that the prepolymer (A-1) solution was changed to the prepolymer (A-8) solution.

Example 9 <Production of Resin Particle (S-9)>
In Example 1, resin particles (S-9) were obtained in the same manner as in Example 1 except that the prepolymer (A-1) solution was changed to the prepolymer (A-9) solution.

Example 10 <Production of Resin Particles (S-10)>
In a beaker, 170 parts by weight of ion-exchanged water, 10.3 parts by weight of [fine particle dispersion], 1 part by weight of sodium carboxymethylcellulose, 48.5% by weight aqueous solution of “dolemyl diphenyl ether disulfonate” “ELEMINOL MON-7” [Sanyo Chemical Industries Co., Ltd.] 36 parts by weight and 15 parts by weight of ethyl acetate were added and stirred to dissolve uniformly.
Next, 67 parts by weight of the non-crystalline polyester resin (L-1), 40 parts by weight of [colorant dispersion], 39 parts by weight of [release agent dispersion] and 54 parts by weight of ethyl acetate are added, and the toner is stirred. 27 parts by weight of the prepolymer (A-5) solution and 0.34 parts by weight of isophoronediamine (B-1) are added to the resin solution in which the binder is uniformly dissolved, and 2 times at 10,000 rpm with a TK auto homomixer. Stir for minutes. 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 resin particles. , Washed and filtered, and dried at 40 ° C. for 18 hours to make the volatile content 0.5% by weight or less. Next, 1.0 part of colloidal silica (“Aerosil R972” manufactured by Nippon Aerosil Co., Ltd.) as an external additive is mixed with 100 parts of toner particles in a sample mill, washed, filtered, and dried at 40 ° C. for 18 hours. Resin particles (S-10) of the present invention were obtained with a volatile content of 0.5 wt% or less.

Example 11 <Production of Resin Particles (S-11)>
In a beaker, 170 parts by weight of ion-exchanged water, 0.3 parts by weight of [fine particle dispersion], 1 part by weight of sodium carboxymethyl cellulose, 48.5% by weight aqueous solution of “doleminol MON-7” [Sanyo Chemical Industries] Co., Ltd.] 36 parts by weight and 15 parts by weight of ethyl acetate were added and stirred to dissolve uniformly.
Next, 63 parts by weight of the non-crystalline polyester resin (L-1), 40 parts by weight of [crystalline polyester resin (M-1) dispersion] obtained in Production Example 14, 40 parts by weight of [colorant dispersion] [Mold release agent dispersion] 39 parts by weight and 54 parts by weight of ethyl acetate were added and stirred to a resin solution in which the toner binder was uniformly dissolved, 27 parts by weight of prepolymer (A-5) solution and isophoronediamine (B -1) 0.17 part by weight was charged and stirred for 2 minutes at 10,000 rpm with a TK auto homomixer. 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 resin particles. , Washed and filtered, and dried at 40 ° C. for 18 hours to make the volatile content 0.5% by weight or less. Next, 1.0 part of colloidal silica (“Aerosil R972” manufactured by Nippon Aerosil Co., Ltd.) as an external additive is mixed with 100 parts of toner particles in a sample mill, washed, filtered, and dried at 40 ° C. for 18 hours. Resin particles (S-10) of the present invention were obtained with a volatile content of 0.5 wt% or less.

Example 12 <Production of Resin Particles (S-12)>
In Example 11, resin particles (S-12) were obtained in the same manner as in Example 14 except that 0.17 part by weight of isophoronediamine (B-1) was changed to 0.12 part by weight of hexamethylenediamine (B-2). Got.

Example 13 <Production of Resin Particles (S-13)>
In Example 11, resin particles (S-13) were prepared in the same manner as in Example 14 except that 0.17 part by weight of isophoronediamine (B-1) was changed to 0.27 part by weight of the blocked amine compound (B-3). )

Example 14 <Production of Resin Particles (S-14)>
In a beaker, 170 parts by weight of ion-exchanged water, 0.3 part by weight of [fine particle dispersion], 1 part by weight of sodium carboxymethyl cellulose, 48.5% by weight aqueous solution of sodium dodecyldiphenyl ether disulfonate (“ELEMINOL MON-7”; Sanyo Kasei) 36 parts by weight of Kogyo Co., Ltd. and 15 parts by weight of ethyl acetate were added and stirred to dissolve uniformly.
Next, 71 parts by weight of an amorphous polyester resin (L-1), 40 parts by weight of [colorant dispersion], 39 parts by weight of [release agent dispersion] and 54 parts by weight of ethyl acetate are added, and the toner is stirred. 18 parts by weight of the prepolymer (A-5) solution was added to the resin solution in which the binder was uniformly dissolved, and the mixture was stirred for 2 minutes at 10,000 rpm with a TK auto homomixer.
The mixture was then aged at 45 ° C. for 48 hours, then transferred to a reaction vessel equipped with a stirrer and a thermometer, and at 50 ° C. until the residual ethyl acetate concentration was 0.5 wt% or less. Was distilled off to obtain an aqueous resin dispersion of resin particles, followed by washing, filtering, and drying at 40 ° C. for 18 hours to make the volatile content 0.5% by weight or less. Next, 1.0 part of colloidal silica (“Aerosil R972” manufactured by Nippon Aerosil Co., Ltd.) as an external additive is mixed with 100 parts of toner particles in a sample mill, washed, filtered, and dried at 40 ° C. for 18 hours. Resin particles (S-14) of the present invention were obtained with a volatile content of 0.5 wt% or less.

Example 15 <Production of Resin Particles (S-15)>
In a beaker, 170 parts by weight of ion-exchanged water, 10.3 parts by weight of [fine particle dispersion], 1 part by weight of sodium carboxymethylcellulose, 48.5% by weight aqueous solution of “dolemyl diphenyl ether disulfonate” “ELEMINOL MON-7” [Sanyo Chemical Industries Co., Ltd.] 36 parts by weight and 15 parts by weight of ethyl acetate were added and stirred to dissolve uniformly.
Next, 50 parts by weight of the non-crystalline polyester resin (L-1), 40 parts by weight of [colorant dispersion], 39 parts by weight of [release agent dispersion] and 54 parts by weight of ethyl acetate are added, and the toner is stirred. 63 parts by weight of the prepolymer (A-10) solution and 1.27 parts by weight of isophoronediamine (B-1) are added to the resin solution in which the binder is uniformly dissolved, and 2 at 10,000 rpm with a TK auto homomixer. Stir for minutes. 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 resin particles. , Washed and filtered, and dried at 40 ° C. for 18 hours to make the volatile content 0.5% by weight or less. Next, 1.0 part of colloidal silica (“Aerosil R972” manufactured by Nippon Aerosil Co., Ltd.) as an external additive is mixed with 100 parts of toner particles in a sample mill, washed, filtered, and dried at 40 ° C. for 18 hours. Resin particles (S-15) of the present invention were obtained with a volatile content of 0.5 wt% or less.

Example 16 <Production of Resin Particles (S-16)>
In a beaker, 170 parts by weight of ion-exchanged water, 10.3 parts by weight of [fine particle dispersion], 1 part by weight of sodium carboxymethylcellulose, 48.5% by weight aqueous solution of “dolemyl diphenyl ether disulfonate” “ELEMINOL MON-7” [Sanyo Chemical Industries Co., Ltd.] 36 parts by weight and 15 parts by weight of ethyl acetate were added and stirred to dissolve uniformly.
Next, 78 parts by weight of the non-crystalline polyester resin (L-1), 40 parts by weight of [colorant dispersion], 39 parts by weight of [release agent dispersion] and 54 parts by weight of ethyl acetate are added, and the toner is stirred. 5 parts by weight of the prepolymer (A-11) solution and 0.01 parts by weight of isophoronediamine (B-1) are added to the resin solution in which the binder is uniformly dissolved, and 2 times at 10,000 rpm with a TK auto homomixer. Stir for minutes. 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 resin particles. , Washed and filtered, and dried at 40 ° C. for 18 hours to make the volatile content 0.5% by weight or less. Next, 1.0 part of colloidal silica (“Aerosil R972” manufactured by Nippon Aerosil Co., Ltd.) as an external additive is mixed with 100 parts of toner particles in a sample mill, washed, filtered, and dried at 40 ° C. for 18 hours. Resin particles (S-16) of the present invention were obtained with a volatile content of 0.5 wt% or less.

Example 17 <Production of Resin Particles (S-17)>
In a beaker, 170 parts by weight of ion-exchanged water, 10.3 parts by weight of [fine particle dispersion], 1 part by weight of sodium carboxymethylcellulose, 48.5% by weight aqueous solution of “dolemyl diphenyl ether disulfonate” “ELEMINOL MON-7” [Sanyo Chemical Industries Co., Ltd.] 36 parts by weight and 15 parts by weight of ethyl acetate were added and stirred to dissolve uniformly.
Next, 71 parts by weight of an amorphous polyester resin (L-1), 40 parts by weight of [colorant dispersion], 39 parts by weight of [release agent dispersion] and 54 parts by weight of ethyl acetate are added, and the toner is stirred. 18 parts by weight of the prepolymer (A-12) solution and 0.17 parts by weight of isophoronediamine (B-1) are added to the resin solution in which the binder is uniformly dissolved, and 2 times at 10,000 rpm with a TK auto homomixer. Stir for minutes. 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 resin particles. , Washed and filtered, and dried at 40 ° C. for 18 hours to make the volatile content 0.5% by weight or less. Next, 1.0 part of colloidal silica (“Aerosil R972” manufactured by Nippon Aerosil Co., Ltd.) as an external additive is mixed with 100 parts of toner particles in a sample mill, washed, filtered, and dried at 40 ° C. for 18 hours. Resin particles (S-17) of the present invention were obtained with a volatile content of 0.5 wt% or less.

Example 18 <Production of resin particles (S-18)>
Example 17 is the same as Example 17 except that the prepolymer (A-12) solution is changed to a prepolymer (A-13) solution and 0.17 parts by weight of isophoronediamine (B-1) is changed to 0.12 parts by weight. In the same manner as above, resin particles (S-18) were obtained.

Example 19 <Production of Resin Particles (S-19)>
Example 17 is the same as Example 17 except that the prepolymer (A-13) solution is changed to a prepolymer (A-14) solution and 0.17 parts by weight of isophoronediamine (B-1) is changed to 0.52 parts by weight. In the same manner as above, resin particles (S-19) were obtained.

Example 20 <Production of Resin Particles (S-20)>
Example 17 is the same as Example 17 except that the prepolymer (A-13) solution is changed to a prepolymer (A-15) solution and 0.17 parts by weight of isophoronediamine (B-1) is changed to 0.51 parts by weight. In the same manner as above, resin particles (S-20) were obtained.

Comparative Example 1 <Production of Resin Particles (S′-1)>
Example 10 is the same as Example 10 except that the prepolymer (A-1) solution is changed to a prepolymer (A′-1) solution and the weight part of isophoronediamine (B-1) is changed to 0.20 part by weight. Similarly, resin particles (S′-1) were obtained.

Comparative Example 2 <Production of Resin Particles (S′-2)>
Example 10 is the same as Example 10 except that the prepolymer (A-1) solution is changed to a prepolymer (A′-2) solution and the weight part of isophoronediamine (B-1) is changed to 0.31 part by weight. Similarly, resin particles (S′-2) were obtained.

Comparative Example 3 <Production of Resin Particles (S′-3)>
Example 10 is the same as Example 10 except that the prepolymer (A-1) solution is changed to a prepolymer (A′-3) solution and the weight part of isophoronediamine (B-1) is changed to 0.31 part by weight. Similarly, resin particles (S′-3) were obtained.

Comparative Example 4 <Production of Resin Particles (S′-4)>
Example 10 is the same as Example 10 except that the prepolymer (A-1) solution is changed to prepolymer (A′-4) and the weight part of isophoronediamine (B-1) is changed to 0.03 part by weight. Thus, resin particles (S′-4) were obtained.

Comparative Example 5 <Production of Resin Particles (S′-5)>
Example 10 is the same as Example 10 except that the prepolymer (A-1) solution is changed to a prepolymer (A′-5) solution and the weight part of isophoronediamine (B-1) is changed to 0.53 parts by weight. Similarly, resin particles (S′-5) were obtained.

Comparative Example 6 <Production of Resin Particles (S′-6)>
In a beaker, 170 parts by weight of ion-exchanged water, 0.3 parts by weight of [fine particle dispersion], 1 part by weight of sodium carboxymethyl cellulose, 48.5% by weight aqueous solution of “doleminyl MON-7”, “ELEMINOL MON-7” [Sanyo Chemical Industries Co., Ltd.] 36 parts by weight and 15 parts by weight of ethyl acetate were added and stirred to dissolve uniformly.
Next, 71 parts by weight of an amorphous polyester resin (L-1), 40 parts by weight of [colorant dispersion], 39 parts by weight of [release agent dispersion] and 54 parts by weight of ethyl acetate are added, and the toner is stirred. 18 parts by weight of the prepolymer (A′-6) solution was added to the resin solution in which the binder was uniformly dissolved, and the mixture was stirred for 2 minutes at 10,000 rpm with a TK auto homomixer.
Subsequently, this mixed liquid was transferred to a reaction vessel equipped with a stirrer and a thermometer, and at 50 ° C., ethyl acetate was distilled off until the residual concentration of ethyl acetate was 0.5% by weight or less. After obtaining the body, it was washed, filtered, and dried at 40 ° C. for 18 hours to make the volatile content 0.5% by weight or less. Next, 1.0 part of colloidal silica (“Aerosil R972” manufactured by Nippon Aerosil Co., Ltd.) as an external additive is mixed with 100 parts of toner particles in a sample mill, and aged at 45 ° C. for 48 hours, then washed and filtered. Then, drying was carried out at 40 ° C. for 18 hours to obtain a resin particle (S′-6) with a volatile content of 0.5% by weight or less.

  For the resin particles (S-1) to (S-20) and (S′-1) to (S′-6), the volume average particle size and particle size distribution are measured by the following method, and the low temperature fixability and hot offset resistance are measured. Property and glossiness were evaluated. The results are shown in Table 3.

<Volume average particle size, particle size distribution>
Resin particles (S-1) to (S-20) and (S′-1) to (S′-6) are dispersed in water, and volume averaged particles are obtained using a Coulter counter “Multisizer III” (manufactured by Beckman Coulter, Inc.). The diameter and particle size distribution were measured.

<Low temperature fixability>
The toner is uniformly placed on the paper so as to be 0.8 mg / cm ² . At this time, as a method of placing the powder 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 uniformly loaded with the above-described 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.
In general, 125 ° C. or lower is preferable under these evaluation conditions.

<Hot offset resistance (hot offset temperature)>
Fixation was evaluated in the same manner as the low-temperature fixability, and the presence or absence of hot offset on the fixed image was visually evaluated.
The temperature at which hot offset occurred after passing through the pressure roller was defined as hot offset resistance (° C.).
In general, 170 ° C. or higher is preferable under these evaluation conditions.

<Glossiness>
Fixation evaluation is performed in the same manner as low-temperature fixability. White cardboard was laid under the image, and the glossiness (%) of the printed image was measured at an incident angle of 60 degrees using a gloss meter (“IG-330” manufactured by Horiba, Ltd.).
Higher gloss means better gloss.
In general, 15% or more is preferable under these evaluation conditions.

The resin particles of Examples 1 to 20 of the present invention exhibited excellent performances in terms of low-temperature fixability, hot offset resistance, and glossiness.
On the other hand, the resin particles of Comparative Example 7 obtained by subjecting a prepolymer (A′-1) obtained without using a trivalent or higher polyisocyanate (D2) together with an amine to stretch have poor offset resistance. Similarly, the resin particles of Comparative Example 8 and Comparative Example 9 in which the prepolymers (A′-2) and (A′-2) obtained without using trivalent or higher polyisocyanate (D2) in combination were subjected to amine elongation, The glossiness is poor.
Moreover, although the polyisocyanate (D2) more than trivalence is used together, the prepolymer (A'-) whose molar ratio (D1) / (D2) of polyisocyanate (D2) and diisocyanate (D1) is less than 1 The resin particles of Comparative Example 10 obtained by elongating 4) have poor gloss, while the resin of Comparative Example 11 obtained by elongating a prepolymer (A′-5) in which (D1) / (D2) exceeds 40 is used. The particles have poor offset resistance.
Furthermore, the glossiness of the resin particles of Comparative Example 12 using the prepolymer (A′-6) containing no polyurethane urea was poor.

  The toner binder and resin particles of the present invention have both low-temperature fixability and hot offset resistance, and are excellent in glossiness. Toner and toner binder for developing electrostatic images used for electrophotography, electrostatic recording, electrostatic printing, etc. Is useful as

Claims (12)

A toner binder containing a polyurethane urea (C) formed by a reaction of a prepolymer (A) having an isocyanate group (d) with an amine compound (B) and / or water,
The prepolymer (A) is a prepolymer obtained by reacting diisocyanate (D1), trivalent or higher polyisocyanate (D2) and polyol (E) as constituent raw materials,
A toner binder, wherein a molar ratio (D1) / (D2) of diisocyanate (D1) to tri- or higher polyisocyanate (D2) is 1.0 to 40.0. The prepolymer (A) molecular weight distribution W _A and polyol (E) of the molecular weight distribution W _E and is claimed in claim 1, wherein the toner binder satisfies the following relationship (1).
1.5 ≦ W _A −W _E ≦ 5.0 (1)
[W _A is calculated by weight average molecular weight (Mw _A ) / number average molecular weight (Mn _A ) of the prepolymer (A), and W _E is weight average molecular weight (Mw _E ) / number average molecular weight of the polyol (E). Calculated as (Mn _E ). ] Of the isocyanate groups (d) in the prepolymer (A), the content (% by weight) of the isocyanate groups (d1) derived from the diisocyanate (D1) based on the weight of the prepolymer (A) and the trivalent or higher The toner binder according to claim 1 or 2, wherein the content (% by weight) of the isocyanate group (d2) derived from the polyisocyanate (D2) satisfies the following relational expression (2).
0.6 ≦ d1 / (d1 + d2) ≦ 1.0 (2) (1) When the polyisocyanate (D2) having three or more valences is a polyisocyanate derived from an aromatic diisocyanate, the diisocyanate (D1) is an aliphatic diisocyanate and / or an alicyclic diisocyanate,
(2) The toner binder according to any one of claims 1 to 3, wherein when the tri- or higher polyisocyanate (D2) is a polyisocyanate derived from an aliphatic diisocyanate, the diisocyanate (D1) is an alicyclic diisocyanate.   The toner binder according to any one of claims 1 to 4, wherein the polyol (E) contains a polyester polyol (E1) obtained by polycondensation of the polyol component (x) and the polycarboxylic acid component (y).   One or more polyisocyanates selected from the group consisting of a compound (D21) having an isocyanurate structure, a compound (D22) having a biuret structure, and a compound (D23) having an adduct structure. The toner binder according to claim 1, wherein   The toner binder according to claim 1, wherein the urethane group concentration of the prepolymer (A) is 1.0 to 8.0% by weight based on the weight of the prepolymer (A).   The toner binder according to claim 1, further comprising an amorphous polyester resin (L).   The toner binder according to any one of claims 1 to 8, wherein the content of the polyurethane urea (C) is 0.1 to 50% by weight based on the weight of the toner binder.   Resin particles comprising the toner binder according to claim 1.   The method for producing a toner binder according to any one of claims 1 to 9, wherein a reaction product of a polyol (E) and a tri- or higher polyisocyanate (D2) is reacted with a diisocyanate (D1). A method for producing a toner binder, comprising a step of obtaining a containing prepolymer (A). The method for producing a toner binder according to any one of claims 1 to 9, comprising a step of reacting a polyol (E), a tri- or higher polyisocyanate (D2) and a diisocyanate (D1), and the following condition (1): Or the manufacturing method of the toner binder which is conditions (2).
(1) When the polyisocyanate (D2) having three or more valences is a polyisocyanate derived from an aromatic diisocyanate, the isocyanate (D1) uses an aliphatic diisocyanate and / or an alicyclic diisocyanate.
(2) When the trivalent or higher polyisocyanate (D2) is a polyisocyanate derived from an aliphatic diisocyanate, the diisocyanate (D1) uses an alicyclic diisocyanate.