JP6404390B2 - Toner binder manufacturing method and resin particle manufacturing method - Google Patents

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 the reaction of a prepolymer (A) containing an isocyanate group (e) with an amine compound (B) and / or water, The prepolymer (A) is obtained by reacting a diol (D1) having a number average molecular weight of 1,000 to 15,000, a tri- or higher valent polyol (D2), and a diisocyanate (E) as constituent raw materials. a is a diol (D1) and trivalent or more polyols (D2) and the molar ratio of (D1) / (D2) is Ri der 2.0 to 25.0, the prepolymer (a) is the diol ( Tonabaida manufacturing method, characterized in that D1) and the polyol (D2) and the collectively a diisocyanate (E) is obtained by reacting; toner binder A method for producing a resin particle comprising a.

  The resin particles containing the toner binder of the present invention have the effect that it is possible to satisfy the three performances of low temperature fixability, hot offset resistance and glossiness which are difficult to achieve at the same time.

Hereinafter, the toner binder of the present invention will be described.
The toner binder of the present invention contains polyurethane urea (C) as an essential component, and (C) is obtained by an extension reaction of the prepolymer (A) containing an isocyanate group (e) with the amine compound (B) and / or water. It is formed. And this prepolymer (A) reacts by making three components of diol (D1) whose number average molecular weight is 1,000-15,000, a trivalent or more polyol (D2), and diisocyanate (E) into a constituent raw material. And a molar ratio (D1) / (D2) between the diol (D1) and the trivalent or higher valent polyol (D2) is 2.0 to 25.0. .

  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) containing the isocyanate group (e) and the amine compound (B), or the prepolymer (A) and water. It is formed by the elongation reaction. The amine compound (B) and water may be used in combination.

  The prepolymer (A) containing the isocyanate group (e) of the present invention has a diol (D1) having a number average molecular weight of 1,000 to 15,000, a trivalent or higher polyol (D2), a diisocyanate (E), Is obtained as a constituent material.

Examples of the diol (D1) that is a constituent material of the prepolymer (A) 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);
Alkylene ether glycols such as 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);
Alkylene oxide of the alicyclic diol (hereinafter, “alkylene oxide” may be abbreviated as AO) adduct (addition mole number 2 to 100) [for example, ethylene oxide of 1,4-cyclohexanedimethanol (hereinafter, “Ethylene oxide” may be abbreviated as EO.) 10 mol adducts and the like]; bisphenols having 13 to 30 carbon atoms (such as bisphenol A, bisphenol F and bisphenol S) or polyphenols having 12 to 24 carbon atoms (for example, Catechol, hydroquinone, resorcin, etc.) AO [EO, propylene oxide (hereinafter, “propylene oxide” may be abbreviated as PO) and butylene oxide, etc.)] adduct (addition mole number 2-100) (for example, bisphenol A -EO 2-4 mol adduct and bisphe Lumpur A · PO2~4 mole adduct);
Polylactone diol (for example, poly-ε-caprolactone diol); polybutadiene diol; polyester diol; and polycarbonate, polyisoprene polyol, hydrogenated polyisoprene polyol, and the like.

  Among the diols (D1), AO addition of polyester diol (D11) obtained by polycondensation of diol component (x) and dicarboxylic acid component (y), alkylene ether glycol, and bisphenols having 13 to 30 carbon atoms is preferred. Among them, polyester diol (D11) is particularly preferable.

  Here, the polyester diol (D11) is a diol having two hydroxyl groups at the terminals in the polyester obtained by polycondensation of the diol component (x) and the dicarboxylic acid component (y).

  As the diol component (x) which is a constituent raw material of the polyester diol (D11), those exemplified for the diol (D1) described above can be used.

  Examples of the dicarboxylic acid component (y) that is a constituent raw material of the polyester diol (D11) include alkane dicarboxylic acids having 4 to 32 carbon atoms (for example, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, etc. Alkene dicarboxylic acid having 4 to 32 carbon atoms (eg, maleic acid, fumaric acid, citraconic acid, mesaconic acid, etc.); branched alkene dicarboxylic acid having 8 to 40 carbon atoms [eg, dimer acid, alkenyl succinic acid (dodecenyl succinic acid, pentane) Decenyl succinic acid and octadecenyl succinic acid); branched alkanedicarboxylic 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 (eg phthalic acid, Le acid, terephthalic acid and naphthalenedicarboxylic acid) and the like.

  The number average molecular weight of the diol (D1) is 1,000 to 15,000, preferably 1,100 to 12,000, and more preferably 1,200 to 10,000. When the number average molecular weight is less than 1000, the hot offset resistance deteriorates, and when it exceeds 15,000, the glossiness deteriorates.

The trivalent or higher valent polyol (D2) is an aliphatic polyhydric alcohol having 3 to 8 or higher valences of 3 to 10 carbon atoms (for example, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitan, sorbitol, etc.). ;
C2-C4 alkylene oxide (hereinafter, “alkylene oxide” may be abbreviated as AO) adduct (addition mole number 2-100) (for example, trisphenol-ethylene) 2-4 mol adducts (hereinafter, “ethylene oxide” may be abbreviated as EO) and trisphenol PA / propylene oxide (hereinafter, “propylene oxide” may be abbreviated as PO) 2 ~ 4 mol adducts etc.);
AO (carbon number 2 to 4) adducts (addition mole number 2 to 100) (phenol novolac PO 2 mol adduct and phenol novolac EO 4 mol adduct) of novolak resins having a polymerization degree of 3 to 50 (for example, phenol novolak and cresol novolak) );
AO (carbon number 2 to 4) adduct (addition mol number 2 to 100) (pyrogallol EO 4 mol adduct) of polyphenols having 6 to 30 carbon atoms (for example, pyrogallol, phloroglucinol and 1,2,4-benzenetriol, etc.) );
Polyester polyol (for example, polyester polyol of diol component (x) and polycarboxylic acid, polyester polyol of dicarboxylic acid component (y) and polyol, and polyester polyol of polyol and polycarboxylic acid);
And acrylic polyol {a copolymer of hydroxyethyl (meth) acrylate and another monomer having a polymerizable double bond [for example, a copolymer of styrene, (meth) acrylic acid and (meth) acrylic acid ester, etc.]}, etc. Can be mentioned.

  Of the polyols (D2), preferred are aliphatic polyhydric alcohols, polyester polyols, and AVO adducts of novolac resins, more preferred are aliphatic polyhydric alcohols, and particularly preferred are glycerin and trimethylolethane. , Trimethylolpropane, pentaerythritol, dipentaerythritol.

As for the ratio of the diol (D1) and the polyol (D2), the molar ratio (D1) / (D2) of the diol (D1) and the polyol (D2) is usually 2.0 to 25.0, preferably 3.0 to 23. 0, more preferably 5.0 to 20.0.
When (D1) / (D2) is less than 2.0, glossiness deteriorates, and when (D1) / D2) exceeds 25.0, hot offset resistance deteriorates.

  Examples of the diisocyanate (E) 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.

  The urethane group concentration in the prepolymer (A) is usually 1.0 to 10.0% by weight, preferably 1.2 to 9.0% by weight, more preferably 2.0 to 8.0% by weight. %. If the urethane group concentration is low, the hot offset resistance deteriorates, and if it is high, the glossiness deteriorates.

  The amine compound (B) that undergoes elongation reaction with the prepolymer (A) is preferably a bifunctional or higher polyamine (B1).

Examples of the bifunctional or higher polyamine (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.
Examples of such a blocked amine compound (B2) include ketimine compounds and oxazolidine obtained by reacting the bifunctional or higher polyamine (B1) with ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), for example. 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 react at 40 to 50 ° C. for 24 hours or more. .

As the mixing ratio of the amine compound (B) or water and the isocyanate group-containing prepolymer (A), the equivalent ratio of the isocyanate group in the isocyanate group-containing prepolymer (A) and active hydrogen in the amine compound (B) or water Is [NCO] / [H], usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2. is there. In addition, when extending | stretching reaction with water, water is handled as a bivalent active hydrogen containing compound.
When [NCO] / [H] exceeds 2 or less than 1/2, the hot offset resistance deteriorates.

The Mw of the isocyanate group-containing prepolymer (A) is usually 10,000 to 300,000, preferably 15,000 to 250,000, more preferably 20,000 to 200, from the viewpoint of hot offset resistance and gloss. , 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 (Mw) of dividing by the molecular weight distribution obtained by the number-average molecular weight (Mn) of the prepolymer (A) and _{(W A),} the difference between the molecular weight distribution of the diol _{(D1) (W} D1) The toner binder of the present invention preferably satisfies the following relational expression (1).
1.5 ≦ W _A −W _D1 ≦ 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), W D1} is weight average molecular weight of the diol _{(D1) (Mw} D1) / number average molecular weight Calculated as (Mn _D1 ).

The value of W _A −W _D1 is usually 1.5 ≦ W _A −W _D1 ≦ 5.0, preferably 1.8 ≦ W _A −W _D1 ≦ 4.0, more preferably 2.0 ≦ W _A. -W _D1 ≤3.5. If the value of W _A -W _D1 is less than 1.5 may hot offset resistance _{deteriorates,} there is a case where the value of W A _{-W D1} is greater than 4.0 and glossiness deteriorates.

The polyurethane urea (C) content of the present invention is the total amount of the prepolymer (A) and the amine compound (B) based on the weight of the toner binder. The toner binder is a total amount obtained by further adding an amorphous resin (L) and a crystalline resin (M) described later to the polyurethane urea (C).
The content of the polyurethane urea (C) is preferably 0.1 to 50% by weight, more preferably 3.0 to 40% by weight based on the weight of the toner binder, from the viewpoint of hot offset resistance and gloss. Preferably it is 5.0-30 weight%.

In the toner binder of the present invention, an amorphous polyester resin (L) that does not react with either the prepolymer (A) containing the isocyanate group (e) or the amine compound (B) can be used in combination.
By using this non-crystalline polyester resin (L) in combination, the low-temperature fixability and gloss are improved, and a prepolymer (A) containing an isocyanate group (e) is formed by an extension reaction with an amine compound and / or water. The polyurethane urea (C) is preferably used 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 non-crystalline polyester resin (L), it is preferable from the viewpoint of low-temperature fixability that the toner binder of the present invention further contains a crystalline resin (M).

  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 crystalline resin (M) contained for this purpose 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 used in an electrophotographic apparatus that employs a heat fixing system as a fixing system, and contain the toner binder of the present invention.
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 for resin particles 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 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 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.
The content of the colorant is preferably 0 to 60% by weight, more preferably 0.1 to 55% by weight, and particularly preferably 0.5 to 50% by weight based on the weight of the resin particles.
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 resin particles.
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 resin particles. .
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 resin particles.

  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 resin particles are obtained by the emulsion phase inversion method, the components constituting the resin particles excluding the fluidizing agent are dissolved or dispersed in an organic solvent, and then emulsified by adding water, etc., and then separated and classified for production. Can do. 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.

  The method for producing a toner binder of the present invention comprises a toner containing a polyurethane urea (C) formed by an extension reaction of a prepolymer (A) containing an isocyanate group (e) with an amine compound (B) and / or water. In the method for producing a binder, an isocyanate group (e) is prepared by reacting a diol (D1) of 1,000 to 15,000 with a diisocyanate (E) and a trivalent or higher polyol (D2). A step of obtaining a prepolymer (A) to be contained.

  The toner binder obtained in the above step is preferable because the distance between cross-linking points is constant, the low-temperature fixability and the hot offset resistance are compatible, and the glossiness is excellent.

  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 Diol (D1-1)>
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 diol (D1-1).
The diol (D1-1) 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 Diols (D1-2) to (D1-4)>
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 the diol (D1-2 ) To (D1-4) were obtained.

Production Example 5 <Synthesis of Diol (D1-5)>
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), adipic acid 298 parts by weight (50.1 moles) and 0.5 parts by weight of titanium diisopropoxybistriethanolamate as a condensation catalyst are added, then the temperature is gradually raised to 220 ° C., and a nitrogen stream is generated at 220 ° C. The reaction was carried out for 4 hours while distilling off 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 diol (D1-5).
The diol (D1-5) 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 Diol (D1-6)>
A polyhydric alcohol and a polycarboxylic acid described in Table 1 were charged into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, and the reaction was conducted in the same manner as in Production Example 1 except that the diol (D1-6 )

Production Example 7 <Synthesis of Diol (D1-7)>
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 5 except that the diol (D1-6 )

Production Example 8 <Synthesis of Diol (D1′-1)>
A polyhydric alcohol and a polycarboxylic acid described in Table 1 were charged into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, and the reaction was conducted in the same manner as in Production Example 1 except that the diol (D1-6 ) In addition, since this (D1'-1) has a number average molecular weight exceeding 15,000, it is used as a raw material of a comparative example.

Production Example 9 <Synthesis of Diol (D1′-2)>
A polyhydric alcohol and a polycarboxylic acid described in Table 1 were charged into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, and the reaction was conducted in the same manner as in Production Example 1 except that the diol (D1-6 ) Since (D1′-1) has a number average molecular weight smaller than 1,000, it is used as a raw material for a comparative example.

Production Examples 10 and 11 <Synthesis of Trivalent or More Polyols (D2-4) and (D2-5)>
A polyhydric alcohol and a polycarboxylic acid described in Table 1 were charged into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and the reaction was conducted in the same manner as in Production Example 1 except that polyol (D2-4 ) And (D2-5) were obtained.

About the diols (D1-1) to (D1-7) and (D1′-1) to (D1′-2), polyols (D2-4) and (D2-5) obtained in Production Examples 1 to 11, The respective compositions and physical property values are shown in Table 1.

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, 447 parts by weight of polyol (D1-1), 1.2 parts by weight of trimethylolpropane, 52 parts by weight of isophorone diisocyanate (IPDI) (E-1) and acetic acid 500 parts by weight of ethyl 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 2.3, the number average molecular weight was 6,200, the weight average molecular weight was 32,240, and the molecular weight distribution was 5.2.

Production Examples 10 to 18 <Synthesis of Prepolymer (A-2) Solution to (A-10) Solution>
The diol, polyol, diisocyanate and ethyl acetate listed in Table 2 were charged into a pressure-resistant reaction vessel equipped with a stirrer, a heating / cooling device and a thermometer. Prepolymer (A-2) solution to (A-10) solution containing

  In Table 2, (E-2) is hexamethylene diisocyanate (HDI).

Comparative Production Example 1 <Synthesis of Prepolymer (A′-1) Solution>
447 parts by weight of diol (D1-1), 52 parts by weight of isophorone diisocyanate 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 reacted at 80 ° C. for 10 hours in a sealed state. And a prepolymer (A′-1) solution containing an isocyanate group at the molecular end was obtained.
The urethane group concentration of the prepolymer (A′-1) was 2.0, the number average molecular weight was 6,900, the weight average molecular weight was 25,000, and the molecular weight distribution was 3.6. Note that (A′-1) is used for the resin particles of Comparative Example 1 because no trivalent or higher polyol is used.

Comparative Production Example 2 <Synthesis of Prepolymer (A′-2) Solution>
447 parts by weight of diol (D1-1), 7.2 parts by weight of trimethylolpropane, 52 parts by weight of isophorone diisocyanate and 500 parts by weight of ethyl acetate are charged into a pressure-resistant reaction vessel equipped with a stirrer, a heating / cooling device and a thermometer, The reaction was carried out at 80 ° C. for 10 hours in a sealed state to obtain a prepolymer (A′-2) solution containing an isocyanate group at the molecular end.
The urethane group concentration of the prepolymer (A′-2) was 3.8, the number average molecular weight was 20,000, the weight average molecular weight was 158,000, and the molecular weight distribution was 7.9. In (A′-2), since the molar ratio of (D1) / (D2) is 1.9, it is used for the resin particles of Comparative Example 2.

Comparative Production Example 3 <Synthesis of Prepolymer (A′-3) Solution>
A pressure-resistant reaction vessel equipped with a stirrer, a heating / cooling device, and a thermometer was reacted according to Example 2 using the diol, polyol, diisocyanate, and ethyl acetate listed in Table 2, and a prepolymer containing isocyanate at the molecular end. A polymer (A′-3) solution was obtained. In (A′-3), the molar ratio of (D1) / (D2) is 27.6, so that it is used for Comparative Example 3.

Comparative Production Example 4 <Prepolymer (A′-4) Solution Synthesis>
Using a diol (D1′-1), polyol, diisocyanate, and ethyl acetate listed in Table 2 in a pressure-resistant reaction vessel equipped with a stirrer, a heating / cooling device, and a thermometer, the reaction was performed according to Comparative Example 2, and the molecular terminal To a prepolymer (A′-4) solution containing an isocyanate. In addition, since the number average molecular weight of (A'-4) used diol (D1'-1) is 15,800, it is used for the resin particles of Comparative Example 9.

Comparative Production Example 5 <Prepolymer (A′-5) Solution Synthesis>
447 parts by weight of polyol (D2-4), 79 parts by weight of isophorone diisocyanate 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 reacted at 80 ° C. for 10 hours in a sealed state. And a prepolymer (A′-5) solution containing an isocyanate group at the molecular end was obtained.
The urethane group concentration of the prepolymer (A′-5) was 3.2, the number average molecular weight was 3,300, the weight average molecular weight was 13,860, and the molecular weight distribution was 4.2. In addition, since (A'-5) does not use diol (D1), it is used for the resin particles of Comparative Example 5.

Comparative Production Example 6 <Prepolymer (A′-6) Solution Synthesis>
500 parts by weight of polyol (D2-5) 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. In addition, since (A'-6) does not use diisocyanate, it is used for the resin particles of Comparative Example 6.

Comparative Production Example 7 <Prepolymer (A′-7) Solution Synthesis>
Using a diol (D1′-2), polyol, diisocyanate, and ethyl acetate listed in Table 2 in a pressure-resistant reaction vessel equipped with a stirrer, a heating / cooling device, and a thermometer, the reaction was performed according to Comparative Example 2, and the molecular terminal To a prepolymer (A′-7) solution containing an isocyanate. In addition, since the number average molecular weight of (A'-7) used diol (D1'-2) is 860, it is used for the resin particle of the comparative example 7.

  About prepolymer (A-1)-(A-10) solution obtained by manufacture example 9-18 and comparative manufacture example 1-7, and comparative prepolymer (A'-1)-(A'-7) solution The respective compositions and physical property values are shown in Table 2.

Production Example 19 <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 20 <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 21 <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 22 <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), 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 23 <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 24 <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 25 <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 26 <Production of blocked amine compound (B-3)>
Into a reaction vessel equipped with a stirrer, heating / cooling device, cooling tube and thermometer, 50 parts by weight of isophorone diamine and 300 parts by weight of methyl ethyl ketone are added, and after 5 hours of reaction at 50 ° C., the solvent is removed and the ketimine block is removed. 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 were added and stirred uniformly. 18 parts by weight of the prepolymer (A-1) solution and 0.26 parts by weight of isophoronediamine (B-1) were added to the resin solution dissolved in TK, and the mixture was stirred at 10,000 rpm for 2 minutes with a TK auto homomixer. . Subsequently, this mixed liquid is transferred to a reaction vessel equipped with a stirrer and a thermometer, and ethyl acetate is distilled off at 50 ° C. until the concentration becomes 0.5% by weight or less. Resin particles containing toner binder (T-1) After being obtained, 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 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, the same procedure as in Example 1 was performed except that the prepolymer (A-1) solution was changed to the prepolymer (A-2) solution and the weight part of isophoronediamine (B-1) was changed to 0.19 part by weight. Thus, resin particles (S-2) containing a toner binder (T-2) were obtained.

Example 3 <Production of Resin Particles (S-3)>
Example 9 is the same as Example 1 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 0.42 parts by weight. Thus, resin particles (S-3) containing a toner binder (T-3) were obtained.

Example 4 <Production of Resin Particles (S-4)>
In Example 1, the same procedure as in Example 1 was performed except that the prepolymer (A-1) solution was changed to prepolymer (A-4) and the weight part of isophoronediamine (B-1) was changed to 0.28 part by weight. Thus, resin particles (S-4) containing a toner binder (T-4) were obtained.

Example 5 <Production of Resin Particles (S-5)>
In Example 1, the same procedure as in Example 1 except that the prepolymer (A-1) solution is changed to the prepolymer (A-5) solution, and the weight part of isophoronediamine (B-1) is changed to 0.27 parts by weight. Thus, resin particles (S-5) containing a toner binder (T-5) were obtained.

Example 6 <Production of Resin Particles (S-6)>
In Example 1, the same procedure as in Example 1 was performed except that the prepolymer (A-1) solution was changed to the prepolymer (A-6) solution, and the weight part of isophoronediamine (B-1) was changed to 0.25 parts by weight. Thus, resin particles (S-6) containing a toner binder (T-6) were obtained.

Example 7 <Production of Resin Particles (S-7)>
In Example 1, the same procedure as in Example 1 was conducted except that the prepolymer (A-1) solution was changed to the prepolymer (A-7) solution and the weight part of isophoronediamine (B-1) was changed to 0.26 parts by weight. Thus, resin particles (S-7) containing a toner binder (T-7) were obtained.

Example 8 <Production of Resin Particles (S-8)>
In Example 1, the same procedure as in Example 1 was performed except that the prepolymer (A-1) solution was changed to the prepolymer (A-8) solution and the weight part of isophoronediamine (B-1) was changed to 0.26 parts by weight. Thus, resin particles (S-8) containing a toner binder (T-8) were obtained.

Example 9 <Production of Resin Particles (S-9)>
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 were added and stirred uniformly. 27 parts by weight of the prepolymer (A-8) solution and 0.39 parts by weight of isophoronediamine (B-1) were added to the resin solution dissolved in the solution and stirred at 10,000 rpm for 2 minutes using a TK auto homomixer. .
Next, this mixed solution is transferred to a reaction vessel equipped with a stirrer and a thermometer, and ethyl acetate is distilled off at 50 ° C. until the concentration becomes 0.5% by weight or less. Resin particles containing a toner binder (T-9) After being obtained, 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 was mixed with 100 parts of toner particles in a sample mill to obtain resin particles (S-9) of the present invention.

Example 10 <Production of Resin Particles (S-10)>
In a beaker, 170 parts by weight of ion-exchanged water, 0.3 part by weight of [fine particle dispersion 1], 1 part by weight of sodium carboxymethylcellulose, and 48.5% by weight aqueous solution of “doleminol MON-7” [Sanyo Kasei] Industrial 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 amorphous polyester resin (L-1), 40 parts by weight of [crystalline polyester resin (M-1) dispersion], 40 parts by weight of [colorant dispersion], [release agent dispersion] 39 parts by weight and 54 parts by weight of ethyl acetate were added, and 27 parts by weight of the prepolymer (A-8) solution and 0.26 parts by weight of isophoronediamine (B-1) were added to the resin solution which was uniformly dissolved by stirring. Then, the mixture was stirred for 2 minutes at 10,000 rpm with a TK auto homomixer. Next, this mixed solution is transferred to a reaction vessel equipped with a stirrer and a thermometer, and ethyl acetate is distilled off at 50 ° C. until the concentration becomes 0.5% by weight or less, and resin particles containing a toner binder (T-10). After being obtained, 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 was mixed with 100 parts of toner particles in a sample mill to obtain resin particles (S-10) of the present invention.

Example 11 <Production of Resin Particles (S-11)>
In Example 8, the toner binder (T-11) was changed in the same manner as in Example 8 except that 0.26 part by weight of isophoronediamine (B-1) was changed to 0.18 part by weight of hexamethylenediamine (B-2). Resin particles (S-11) were obtained.

Example 12 <Production of Resin Particles (S-12)>
In Example 8, a toner binder (T-12) was prepared in the same manner as in Example 8 except that 0.26 parts by weight of isophoronediamine (B-1) was changed to 0.42 parts by weight of the blocked amine compound (B-3). ) Resin particles (S-12) were obtained.

Example 13 <Production of Resin Particles (S-13)>
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 were added and stirred uniformly. 18 parts by weight of the prepolymer (A-8) solution was added to the resin solution dissolved in 1, and stirred at 10,000 rpm with a TK auto homomixer for 2 minutes.
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 containing toner binder (T-13), which was then washed, filtered and dried at 40 ° C. for 18 hours, with a volatile content of 0.5% by weight or less. It was. 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 toner particles in a sample mill to obtain resin particles (S-13) of the present invention.

Example 14 <Production of Resin Particles (S-14)>
In Example 1, the same procedure as in Example 1 except that the prepolymer (A-1) solution is changed to the prepolymer (A-9) solution, and the weight part of isophoronediamine (B-1) is changed to 0.27 part by weight. Thus, resin particles (S-14) containing a toner binder (T-14) were obtained.

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, 78 parts by weight of 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 were added and stirred uniformly. 5 parts by weight of the prepolymer (A-10) solution and 0.03 parts by weight of isophoronediamine (B-1) were added to the resin solution dissolved in the solution and stirred at 10,000 rpm for 2 minutes 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, and resin particles containing a toner binder (T-15). After being obtained, 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 was mixed with 100 parts of toner particles by a sample mill to obtain resin particles (S-15) of the present invention.

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, 45 parts by weight of 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 were added and stirred uniformly. 72 parts by weight of the prepolymer (A-3) solution and 1.16 parts by weight of isophorone diamine (B-1) were added to the resin solution dissolved in 1, and stirred at 10,000 rpm for 2 minutes with a TK auto homomixer. .
Next, this mixed solution is transferred to a reaction vessel equipped with a stirrer and a thermometer, and ethyl acetate is distilled off at 50 ° C. until the concentration becomes 0.5% by weight or less. Resin particles containing a toner binder (T-16) After being obtained, it was washed, filtered, and dried at 40 ° C. for 18 hours to make the volatile content 0.5% by weight or less. Subsequently, 100 parts of toner particles were mixed with 1.0 part of colloidal silica (“Aerosil R972” manufactured by Nippon Aerosil Co., Ltd.) as an external additive in a sample mill to obtain resin particles (S-16) of the present invention.

  The resin particles of the present invention can be obtained by using trimethylolethane (D2-6) as the trivalent or higher polyol (D2).

Comparative Example 1 <Production of Resin Particles (S′-1)>
Example 1 is the same as Example 1 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 0.31 part by weight. Similarly, resin particles (S′-1) containing a toner binder (T′-1) were obtained.

Comparative Example 2 <Production of Resin Particles (S′-2)>
Example 1 is the same as Example 1 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 0.06 parts by weight. Similarly, resin particles (S′-2) containing a toner binder (T′-2) were obtained.

Comparative Example 3 <Production of Resin Particles (S′-3)>
Example 1 is the same as Example 1 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 0.29 parts by weight. Similarly, resin particles (S′-3) containing a toner binder (T′-3) were obtained.

Comparative Example 4 <Production of Resin Particles (S′-4)>
In Example 1, the same procedure as in Example 1 was performed except that the prepolymer (A-1) solution was changed to prepolymer (A′-4) and the weight part of isophoronediamine (B-1) was changed to 0.09 part by weight. Thus, resin particles (S′-4) containing a toner binder (T′-4) were obtained.

Comparative Example 5 <Production of Resin Particles (S′-5)>
Example 1 is the same as Example 1 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 0.47 parts by weight. Similarly, resin particles (S′-5) containing a toner binder (T′-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 part by weight of [fine particle dispersion 1], 1 part by weight of sodium carboxymethylcellulose, and 48.5% by weight aqueous solution of “doleminol MON-7” [Sanyo Kasei] Industrial 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, and a toner binder (T′- After obtaining an aqueous resin dispersion of resin particles containing 1), it is aged at 45 ° C. for 48 hours, then washed, filtered, and dried at 40 ° C. for 18 hours, with a volatile content of 0.5% by weight or less. It was. 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 toner particles by a sample mill to obtain resin particles (S′-6).

Comparative Example 7 <Production of Resin Particles (S′-7)>
Example 1 is the same as Example 1 except that the prepolymer (A-1) solution is changed to a prepolymer (A′-7) solution and the weight part of isophoronediamine (B-1) is changed to 0.76 parts by weight. Similarly, resin particles (S′-7) containing a toner binder (T′-7) were obtained.

  For the resin particles (S-1) to (S-16) and (S′-1) to (S′-7), 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-116), (S′-1) to (S′-7) 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 resin particles are 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 9 to 21 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 extending the prepolymer (A′-1) obtained without using the trivalent or higher polyol (D2) in combination have poor offset resistance. Further, a tripolymer or higher polyol (D2) is used in combination, but the molar ratio (D1) / (D2) between the diol (D1) and the polyol (D2) is less than 2 (A′-2) In the resin particles of Comparative Example 8 obtained by extending the amine, the glossiness and the low-temperature fixability were poor, while the (D1) / (D2) of the prepolymer (A′-3) in which the (D1) / (D2) exceeded 25 was subjected to the amine extension. Resin particles have poor offset resistance.
Further, the resin particles of Comparative Example 10 obtained by extending the prepolymer (A′-4) using the diol (D1) having a number average molecular weight exceeding 15,000 with amine, and the prepolymer (A ′) using no diol (D1). The resin particles of Comparative Example 11 obtained by extending the amine of −5) have poor gloss.
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. Resin particles for toner for developing electrostatic images used for electrophotography, electrostatic recording, electrostatic printing, etc. And useful as a toner binder.

Claims (9)

A toner binder containing a polyurethane urea (C) formed by a reaction of an isocyanate group (e) -containing prepolymer (A) with an amine compound (B) and / or water, the prepolymer (A) Is a prepolymer obtained by reacting a diol (D1) having a number average molecular weight of 1,000 to 15,000, a tri- or higher valent polyol (D2), and a diisocyanate (E) as constituent raw materials, the molar ratio of D1) and trivalent or more polyols (D2) (D1) / (D2) is Ri der 2.0 to 25.0, the prepolymer (a) is the diol (D1) and the polyol ( A method for producing a toner binder, wherein D2) and the diisocyanate (E) are reacted together . Method for producing a toner binder of claim 1 wherein the molecular weight distribution W _D1 of the molecular weight distribution W _A and a diol (D1) of the prepolymer (A) satisfies the following relationship (1).
1.5 ≦ W _A −W _D1 ≦ 5.0 (1)
[W _A is calculated by the weight average molecular weight (Mw _A ) / number average molecular weight (Mn _A ) of the prepolymer (A), and W _D1 is the weight average molecular weight (Mw _D1 ) / number average molecular weight of the diol (D1). Calculated as (Mn _D1 ). ] The method for producing a toner binder according to claim 1 or 2, wherein the diol (D1) contains a polyester diol (D11) formed by polycondensation of the diol component (x) and the dicarboxylic acid component (y). The toner binder according to claim 1, wherein the trivalent or higher polyol (D2) contains one or more selected from the group consisting of glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and dipentaerythritol. Manufacturing method . The method for producing a toner binder according to any one of claims 1 to 4, wherein the urethane group concentration of the prepolymer (A) is 1.0 to 10.0% by weight based on the weight of the prepolymer (A). The method for producing a toner binder according to claim 1, wherein the amine compound (B) is a bifunctional or higher functional polyamine (B1). The method for producing a toner binder according to any one of claims 1 to 6, wherein the content of the polyurethane urea (C) is 0.1 to 50% by weight based on the weight of the toner binder. Furthermore, the manufacturing method of the toner binder in any one of Claims 1-7 containing amorphous polyester (L). The manufacturing method of the resin particle containing the toner binder in any one of Claims 1-8.