JP2015083668A - Resin particle, manufacturing method of resin particle, and toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin particle excellent in low temperature fixability and storage stability.SOLUTION: There is provided a resin particle (P) containing a polyester resin (A) having polycarboxylic acid (a1) and polyvalent alcohol (a2) as constitutional units with a weight average molecular weight of (A) of 1,000 to 8,000 and an ester group concentration of (A) of 16 to 30 wt.% based on the weight of (A), and (A) satisfies following condition 1. [Condition 1] 229×(ECON)+90×(OHV)≤12000, where (ECON) represents a value showing the ester group concentration of (A) represented with wt.% unit and (OHV) represents a value showing a hydroxyl group value of (A) represented with mgKOH/g unit.

Description

  The present invention relates to resin particles, a method for producing the same, and a toner.

It is desired that resin particles used in powder coatings and the like are melted with low energy and fixed on a substrate. Therefore, there is a strong demand for resin particles having excellent low-temperature fixability.
As a means for obtaining resin particles having excellent low-temperature fixability, a method of lowering the glass transition temperature of the resin has been disclosed (Patent Document 1). However, the storage stability of the resin particles is deteriorated only by lowering the glass transition temperature, and both low-temperature fixability and storage stability cannot be achieved.

JP2013-37352A

An object of this invention is to provide the resin particle which is excellent in low-temperature fixability and storage stability.

The inventor of the present invention has arrived at the present invention as a result of intensive studies to develop resin particles excellent in low-temperature fixability and storage stability. That is, the present invention is the following three inventions.
[1] Resin particles (P) containing a polyester resin (A) having a polycarboxylic acid (a1) and a polyhydric alcohol (a2) as structural units, wherein the weight average molecular weight of (A) is 1,000 to Resin particles (P) that are 8,000, the ester group concentration of (A) based on the weight of (A) is 16 to 30% by weight, and (A) satisfies the following condition 1.
[Condition 1]
229 × (ECON) + 90 × (OHV) ≦ 12000
[(ECON) represents a numerical value indicating the ester group concentration of (A) expressed in units of wt%, and (OHV) represents a numerical value indicating the hydroxyl value of (A) expressed in units of mgKOH / g. ]
[2] After the step of dispersing the solution (S) obtained by dissolving at least the polyester resin (A) in the organic solvent (U) in the medium (M) to obtain the dispersion (DM), the dispersion (DM ), The organic solvent (U) and the medium (M) are removed from the resin particle (P).
[3] A toner comprising resin particles (P), a colorant and a release agent.

The resin particles (P) of the present invention are excellent in low-temperature fixability and storage stability, particularly storage stability (humidity heat storage stability) in a high-temperature and high-humidity environment.

4 is a flowchart of an experimental apparatus used for manufacturing toner using carbon dioxide in a liquid state or a supercritical state in the present invention.

The polyester resin (A) contained in the resin particles (P) of the present invention has a polycarboxylic acid (a1) and a polyhydric alcohol (a2) as structural units.
As polycarboxylic acid (a1) which becomes a structural unit of polyester resin (A), dicarboxylic acid (a11), tri- or hexavalent or higher polycarboxylic acid (a12), and modification of (a11) or (a12) And the body (a13). In addition, (a1) may be used independently and may use 2 or more types together.

Examples of the dicarboxylic acid (a11) 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 ), And the like.
Of these, alkene dicarboxylic acids and aromatic dicarboxylic acids are preferred, and aromatic dicarboxylic acids are more preferred.

Examples of the tricarboxylic acid having 3 to 6 or more polycarboxylic acids (a12) 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.

Examples of the modified form (a13) of (a11) or (a12) include an acid anhydride of (a11) or (a12) and a lower alkyl ester of (a11) or (a12).
Examples of the acid anhydride (a11) or (a12) include trimellitic anhydride, phthalic anhydride, maleic anhydride, pyromellitic anhydride, and the like.
Examples of the lower alkyl ester of (a11) or (a12) include methyl ester, ethyl ester, and isopropyl ester.

Examples of the polyhydric alcohol (a2) include a diol (a21) and a trivalent to octavalent or higher polyol (a22). In addition, (a2) may be used independently and may use 2 or more types together.

Examples of the diol (a21) include alkylene glycols having 2 to 30 carbon atoms (for example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, octanediol). , Decanediol, dodecanediol, tetradecanediol, neopentyl glycol and 2,2-diethyl-1,3-propanediol, etc.); number average molecular weight (hereinafter abbreviated as Mn) = 106 to 10,000 alkylene ether glycol ( For example, diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol); alicyclic diols having 6 to 24 carbon atoms (for example, 1,4-cyclohexa) Dimethanol, hydrogenated bisphenol A, etc.); alkylene oxide (hereinafter abbreviated as AO) adduct (number of added moles 2 to 100) of Mn = 100 to 10,000 (for example, 1,4-cyclohexane) Dimethanol ethylene oxide (hereinafter abbreviated as EO) 10 mol adduct, etc.]; bisphenols having 13 to 30 carbon atoms (bisphenol A, bisphenol F, bisphenol S, etc.) or polyphenols having 12 to 24 carbon atoms (for example, catechol, Hydroquinone and resorcin etc.) AO [EO, propylene oxide (hereinafter abbreviated as PO) and butylene oxide (hereinafter abbreviated as BO), etc.] adducts (addition mole number 2 to 100) (for example, bisphenol A · EO 2 to 4 mol) Additives and bisphenol A · PO2-4 Weight average molecular weight (hereinafter abbreviated as Mw) = 100-5,000 polylactone diol (for example, poly-ε-caprolactone diol, etc.); Mw = 1,000-20,000 polybutadiene diol, etc. Is mentioned.

As the polyol (a22) 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) (eg phenol novolac PO 2 mol addition) of 3-50 novolak resins (eg phenol novolak and cresol novolak, etc.) And phenol novolac EO 4 mol adduct); polypheno having 6 to 30 carbon atoms (For example, pyrogallol, phloroglucinol and 1,2,4-benzenetriol) AO (2 to 4 carbon atoms) adduct (2 to 100 moles added) (pyrogallol EO 4 mol adduct); and degree of polymerization 20 ˜2,000 acrylic polyol {copolymer of hydroxyethyl (meth) acrylate and other polymerizable double bond monomer [for example, styrene, (meth) acrylic acid and (meth) acrylic ester, etc.] Etc.}.
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 polyhydric alcohols (a2), the diol (a21) is preferable, and more preferable are alkylene glycols having 2 to 30 carbon atoms, AO adducts of bisphenols having 15 to 30 carbon atoms, and combinations thereof. More preferred are alkylene glycols having 2 to 10 carbon atoms, AO adducts of bisphenol A, and combinations thereof. Particularly preferred are ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, neopentyl glycol, AO adducts of bisphenol A and combinations thereof, and most preferred is 1,2-propylene glycol. And an AO adduct of bisphenol A.

When the alkylene glycol and the AO adduct of bisphenols are used in combination, the content of the alkylene glycol in the polyester resin (A) is that of (A) from the viewpoint of low-temperature fixability and wet heat storage stability of the resin particles (P). Based on the weight, it is preferably 3 to 35% by weight, more preferably 4 to 30% by weight, and particularly preferably 5 to 25% by weight.

The polyester resin (A) may further contain a monocarboxylic acid (a3) and / or a monohydric alcohol (a4) as a structural unit in addition to the polycarboxylic acid (a1) and the polyhydric alcohol (a2).
Examples of the monocarboxylic acid (a3) include an aliphatic monocarboxylic acid (a31), an aromatic monocarboxylic acid (a32), and a modified product (a33) of (a31) or (a32). In addition, (a3) may be used independently and may use 2 or more types together.

Examples of the aliphatic monocarboxylic acid (a31) include a chain saturated monocarboxylic acid (a311), a chain unsaturated monocarboxylic acid (a312), and an alicyclic monocarboxylic acid (a313).
As the chain saturated monocarboxylic acid (a311), a linear or branched chain saturated monocarboxylic acid having 2 to 30 carbon atoms (acetic acid, propionic acid, butyric acid, valeric acid, 2-ethylhexanoic acid, caproic acid, enanthate) Acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, tuberculostearic acid, arachidic acid, behenic acid, and lignoceric acid).
As the chain unsaturated monocarboxylic acid (a312), a linear or branched chain unsaturated monocarboxylic acid having 3 to 30 carbon atoms (acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, palmitoleic acid, oleic acid Vacenoic acid, linoleic acid, α-linolenic acid, γ-linolenic acid, eleostearic acid, 8,11-eicosadienoic acid, 5,8,11-eicosatrienoic acid, arachidonic acid, stearidonic acid, eicosapentaenoic acid, Docosapentaenoic acid, docosahexaenoic acid, dihomo-γ-linolenic acid, docosapentaenoic acid, elaidic acid, erucic acid, nervonic acid and the like.

Examples of the alicyclic monocarboxylic acid (a313) include alicyclic monocarboxylic acids having 4 to 14 carbon atoms (such as cyclopropane carboxylic acid, cyclobutane carboxylic acid, cyclopentane carboxylic acid, cyclohexane carboxylic acid, and cycloheptane carboxylic acid). Is mentioned.
Examples of the aromatic monocarboxylic acid (a32) include aromatic monocarboxylic acids having 7 to 36 carbon atoms. Specific examples include benzoic acid, vinyl benzoic acid, toluic acid, dimethyl benzoic acid, and t-butyl benzoic acid. , Cumic acid, naphthoic acid, biphenyl monocarboxylic acid and furic acid.
Of the monocarboxylic acid (a3), the aromatic monocarboxylic acid (a32) is preferred from the viewpoints of low-temperature fixability and wet heat storage stability of the resin particles (P), and more preferred is benzoic acid, t-Butylbenzoic acid and naphthoic acid.

Examples of the modified form (a33) of (a31) or (a32) include the acid anhydride of (a31) or (a32) and the lower alkyl ester of (a31) or (a32).
Examples of the acid anhydride (a31) or (a32) include trimellitic anhydride, phthalic anhydride, maleic anhydride, pyromellitic anhydride, and the like.
Examples of the lower alkyl ester of (a31) or (a32) include methyl ester, ethyl ester, and isopropyl ester.

Examples of the monohydric alcohol (a4) include an aliphatic monohydric alcohol (a41) and an aromatic monohydric alcohol (a42). In addition, (a4) may be used independently and may use 2 or more types together.
Examples of the aliphatic monohydric alcohol (a41) include a chain saturated monohydric alcohol (a411) and a chain unsaturated monohydric alcohol (a412).

As the chain saturated monohydric alcohol (a411), linear or branched chain saturated monohydric alcohol having 1 to 30 carbon atoms (methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, butanol, pentanol, 2-methyl) -1-butanol, 2,2-dimethyl-1-propanol, hexanol, 4-methyl-1-pentanol, 2,3-dimethyl-2-butanol, heptanol, 3-ethyl-3-pentanol, octanol, 2 -Ethyl-1-hexanol, nonanol, 2,6-dimethyl-4-heptanol, decanol, undecanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, and stearyl alcohol), and a linear or branched chain having 1 to 30 carbon atoms AO having 2 to 4 carbon atoms in the formula saturated monohydric alcohol EO, obtained by adding the PO and BO) (number of moles added 20 mol), and the like.

As the chain unsaturated monohydric alcohol (a412), a linear or branched chain unsaturated monohydric alcohol having 2 to 30 carbon atoms (allyl alcohol, 2-buten-1-ol, 2-penten-1-ol 2-hexen-1-ol, 2-hepten-1-ol, 2-octen-1-ol, 2-nonen-1-ol, 2-decen-1-ol, 2-dodecenol, palmitoleyl alcohol, oleyl Alcohol, linoleyl alcohol, etc.), and C1-C30 linear or branched unsaturated monohydric alcohol added with C2-C4 AO (EO, PO, and BO) (addition moles) 1-20 mol) and the like.
Etc.

As aromatic monohydric alcohol (a42), C6-C30 aromatic monohydric alcohol (phenol, ethylphenol, isobutylphenol, pentylphenol, octylphenol, dodecylphenol, tetradecylphenol, benzyl alcohol, etc.), and carbon Examples include those obtained by adding AO (EO, PO, and BO) having 2 to 4 carbon atoms to an aromatic monohydric alcohol having 6 to 30 (addition mole number 1 to 20 mol).

The polyester resin (A) may have a structure in which a vinyl monomer (a5) is grafted as necessary.

Examples of the vinyl monomer (a5) include vinyl esters such as vinyl chloride, vinyl bromide, vinyl iodide, vinyl acetate, vinyl propionate, vinyl formate and vinyl caproate; for example, acrylic acid, methyl acrylate and ethyl acrylate. , N-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, amyl acrylate, cyclohexyl acrylate, n-octyl acrylate, isooctyl acrylate, decyl acrylate, acrylic Lauryl acid, 2-ethylhexyl acrylate, stearyl acrylate, methoxyethyl acrylate, 2-hydroxyethyl acrylate, glycidyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate, Crylic acid, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, amyl methacrylate, cyclohexyl methacrylate, n-octyl methacrylate , Isooctyl methacrylate, decyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, methoxyethyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, methacryl Ethylenic monocarboxylic acids such as diethylaminoethyl acid and esters thereof; for example, ethylenic monomers such as acrylonitrile, methacrylonitrile, acrylamide Nocarboxylic acid substitution products; ethylenic dicarboxylic acids such as dimethyl maleate and substitution products thereof; vinyl ketones such as vinyl methyl ketone; vinyl ethers such as vinyl ethyl ether; vinylidene halides such as vinylidene chloride.

The ratio of the polycarboxylic acid (a1) to the polyhydric alcohol (a2) in the polyester resin (A) is preferably 1 as the equivalent ratio [COOH] / [OH] of the carboxyl group [COOH] and the hydroxyl group [OH]. / 2 to 1/1, more preferably 1 / 1.5-1 to 1/1, and particularly preferably 1 / 1.3-1 to 1.02.

The number average molecular weight Mn of the polyester resin (A) is preferably 1,000 to 8,000, more preferably 1,100 to 6 from the viewpoint of achieving both low temperature fixability and storage stability of the resin particles (P). 1,000, particularly preferably 1,500 to 4,000.
The weight average molecular weight Mw of the polyester resin (A) is 1,000 to 8,000, and preferably 2,000 to 6,500, more preferably 3 from the viewpoint of achieving both low temperature fixability and storage stability of the toner. , 5,000 to 5,500.
Mn and Mw of the resin (A) in the present invention can be measured using gel permeation chromatography (GPC) under the following conditions.
Apparatus (example): “HLC-8120” [manufactured by Tosoh Corporation]
Column (example): “TSK GEL GMH6” [manufactured by Tosoh Corporation] Measurement temperature: 40 ° C.
Sample solution: 0.25% by weight tetrahydrofuran solution (insoluble matter filtered off with glass filter)
Solution injection volume: 100 μl
Detection apparatus: Refractive index detector Reference material: Standard polystyrene (TSK standard POLYSTYRENE) 12 points (Molecular weight: 500, 1,050, 2,800, 5,970, 9,100,
18,100,37,900,96,400,190,000,355,000,
1,090,000, 2,890,000) [manufactured by Tosoh Corporation]

The ester group concentration based on the weight of (A) of the polyester resin (A) is 16 to 30% by weight, preferably 18 to 29% by weight from the viewpoint of heat-resistant storage stability and wet heat-resistant storage stability, The amount is preferably 20 to 28% by weight, particularly preferably 25 to 28% by weight.
The ester group concentration based on the weight of (A) of the polyester resin (A) can be calculated from the number of ester groups [—C (═O) O—] in (A). Specifically, It is a value represented by the following formula.

Ester group concentration (unit:%) = [(N × 44) / number average molecular weight] × 100

Here, N is the average number of ester groups per molecule of the polyester resin (A), and 44 is the formula weight of the ester group [—C (═O) O—].
In calculating the actual ester group concentration, a method for calculating and calculating the monomer composition and the number of ester groups constituting (A) by nuclear magnetic resonance spectrum (NMR) or the like, or the ratio of the raw materials used for the production of (A) There is a method of calculating the number of ester groups from the above.

The polyester resin (A) satisfies the following [Condition 1], and preferably satisfies the following [Condition 2] from the viewpoint of heat-resistant storage stability and moisture-heat storage stability of the resin particles (P). It is preferable that the following [Condition 3] is satisfied.
[Condition 1]
229 × (ECON) + 90 × (OHV) ≦ 12,000
[Condition 2]
229 × (ECON) + 90 × (OHV) ≦ 10,000
[Condition 3]
229 × (ECON) + 90 × (OHV) ≦ 8,500
[(ECON) represents a numerical value indicating the ester group concentration of (A) expressed in units of wt%, and (OHV) represents a numerical value indicating the hydroxyl value of (A) expressed in units of mgKOH / g. ]

The hydroxyl value of the polyester resin (A) is preferably from 10 to 80 mgKOH / g, more preferably from 12 to 65 mgKOH / g, particularly preferably from 15 to 50 mgKOH / g, from the viewpoints of heat resistant storage stability and wet heat resistant storage stability. is there.
In addition, the hydroxyl value of (A) can be measured by the method of JIS K0070-1992.

The acid value of the polyester resin (A) is 0 to 40 mgKOH / g or less, more preferably 0 to 30 mgKOH / g, particularly preferably 1 to 25 mgKOH / g, and most preferably 2 to 20 mgKOH / g.
In addition, the acid value of (A) can be measured by the method of JIS K0070-1992.

  The polyester resin (A) is obtained by storing (A) for 20 hours under the conditions of 40 ° C. and 80% relative humidity (humidity heat resistance test) from the viewpoint of the heat and heat resistance stability of the resin particles (P). ) Is preferably 12,000 ppm or less based on the weight of (A), more preferably 10,000 ppm or less, and particularly preferably 8,500 ppm or less.

  The polyester resin (A) is obtained after storing the polyester resin (A) for 20 hours under the conditions of 40 ° C. and 80% relative humidity from the viewpoint of the heat and heat resistant storage stability of the resin particles (P). (A) Flow tester 1/2 drop temperature (T1) and (A) Flow tester (A) before storing (A) for 20 hours under conditions of 40 ° C. and 80% relative humidity The absolute value of the difference from the ½ drop temperature (T2) is preferably 8 ° C. or less, more preferably 7 ° C. or less, and particularly preferably 6 ° C. or less.

In addition, "1/2 fall temperature" by the flow tester of a polyester resin (A) is measured as follows using a Koka type flow tester [for example, "CFT-500D" made by Shimadzu Corporation].
While heating 1 g of the polyester resin (A) at a heating rate of 6 ° C./min, a load of 1.96 MPa was applied by a plunger and extruded from a nozzle having a diameter of 1 mm and a length of 1 mm. ) Is the temperature at which the temperature drops by a flow tester.
Specifically, a graph is drawn with the axes of “temperature” and “plunger descent amount (flow value)”, and a temperature corresponding to ½ of the maximum value of the plunger descent amount is read from the graph.

From the viewpoint of the glass transition temperature of the polyester resin (A) (hereinafter abbreviated as Tg), the resin particles (P) have low-temperature fixability, heat-resistant storage stability, and heat-and-heat-resistant storage stability in a high-temperature and high-humidity environment. Preferably it is 40-80 degreeC, More preferably, it is 40-70 degreeC, Most preferably, it is 40-60 degreeC.
In addition, Tg of (A) can be measured by the method (DSC) prescribed | regulated to ASTM D3418-82 using "DSC20, SSC / 580" [made by Seiko Instruments Inc.].

The polyester resin (A) can be produced by a known method. Specifically, (A) is produced by polycondensation of polycarboxylic acid (a1) and polyhydric alcohol (a2) and, if necessary, monocarboxylic acid (a3) and / or monohydric alcohol (a4). be able to.
The reaction temperature during polycondensation is preferably 100 to 250 ° C., the reaction pressure is preferably 0.001 to 0.2 MPa, and the reaction time is preferably 1 to 50 hours.
The polycondensation is preferably performed while removing generated water from the reaction system in order to improve the reaction rate.
In order to accelerate the reaction, it is preferable to use a catalyst. Examples of the catalyst include inorganic acids (for example, sulfuric acid and hydrochloric acid), organic sulfonic acids (for example, methanesulfonic acid, paratoluenesulfonic acid, xylenesulfonic acid, naphthalenesulfonic acid, and the like) and organic metal compounds (for example, dibutyltin oxide, tetraisopropoxy). Titanate, bistriethanolamine titanate, potassium oxalate titanate, etc.). When a catalyst is used, the catalyst can be neutralized as necessary after completion of the esterification reaction and treated with an adsorbent to remove and purify the catalyst.

When producing the polyester resin (A) of the present invention, the polycarboxylic acid (a1) and the polyhydric alcohol (a2) are polycondensed to obtain the polyester resin (A), and then included in the polyester resin (A). The step of removing the polyhydric alcohol (a2) having a boiling point of 250 ° C. or lower may be included.
By including the step of removing the polyhydric alcohol (a2) having a boiling point of 250 ° C. or less contained in the polyester resin (A), the obtained resin particles (P) have low temperature fixability, heat-resistant storage stability and moisture-heat-resistant storage. Stability is improved.

Examples of the step of removing the polyhydric alcohol (a2) having a boiling point of 250 ° C. or less contained in the polyester resin (A) include a method of removing by a reduced pressure.
The pressure when the polyhydric alcohol (a2) having a boiling point of 250 ° C. or less contained in the polyester resin (A) is removed under reduced pressure is preferably 0.001 to 0.050 MPa, more preferably 0.002 to 0.002. The pressure is 0.040 MPa, particularly preferably 0.003 to 0.020 MPa.
When removing the polyhydric alcohol (a2) under reduced pressure, it may be removed under heating, preferably 100 to 270 ° C, more preferably 150 to 260 ° C, and particularly preferably 170 to 250 ° C.

The resin particles (P) of the present invention can contain a resin (B) other than the polyester resin (A). Examples of the resin (B) include polyester resin (B1), polyurethane resin (B2), polyurea resin (B3), vinyl resin (B4), and epoxy resin (B5).
In addition, (B) may be used alone or in combination of two or more.
Further, from the viewpoint of further improving the low-temperature fixability of the toner containing the resin particles (P), it is preferable that the resin (B) other than the polyester resin (A) contains a crystalline resin.

The polyester resin (B1) is a polyester resin having a polycarboxylic acid (a1) and a polyhydric alcohol (a2) as constituent units, and the Mw is not in the range of 1,000 to 8,000, the ester group concentration Is not in the range of 16 to 30% by weight, or does not satisfy the above condition 1.

Examples of the polyurethane resin (B2) include the polyester resin (A) and / or the polyhydric alcohol (a2) and a diisocyanate (c), and if necessary, a diamine (b) as a structural unit.

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

Examples of chain aliphatic diamines include alkylene diamines having 2 to 12 carbon atoms (ethylene diamine, propylene diamine, trimethylene diamine, tetramethylene diamine, hexamethylene diamine, and the like).
Cycloaliphatic diamines 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.}.

  Examples of the aromatic diamine having 6 to 20 carbon atoms include 1,2-, 1,3- or 1,4-phenylenediamine, 2,4′- or 4,4′-diphenylmethanediamine, diaminodiphenylsulfone, benzidine, and thiodianiline. Bis (3,4-diaminophenyl) sulfone, 2,6-diaminopyridine, m-aminobenzylamine, naphthylenediamine, 2,4- or 2,6-tolylenediamine, crude tolylenediamine, diethyltolylenediamine Amine, 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, -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′-tetra Isopropyl-4,4′-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′-diaminoben Examples include zophenone, 3,3 ′, 5,5′-tetraethyl-4,4′-diaminodiphenyl ether, 3,3 ′, 5,5′-tetraisopropyl-4,4′-diaminodiphenyl sulfone, and mixtures thereof. It is done.

  As the diisocyanate (c), an aromatic diisocyanate having 6 to 20 carbon atoms (excluding carbon in the NCO group; the same shall apply hereinafter), an aliphatic diisocyanate having 2 to 18 carbon atoms, a modified product of these diisocyanates (urethane group, Carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group and oxazolidone group-containing modified product) and mixtures of two or more thereof.

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

Examples of the aliphatic diisocyanate include a chain aliphatic diisocyanate and a cyclic aliphatic diisocyanate.
Examples of chain aliphatic diisocyanates include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and 2,6-diisocyanatomethylcaproate. Bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate and mixtures thereof.
Cycloaliphatic diisocyanates include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), and bis (2-isocyanatoethyl). -4-cyclohexene-1,2-dicarboxylate, 2,5- or 2,6-norbornane diisocyanate, and mixtures thereof.

  As the modified product of diisocyanate, a modified product containing a urethane group, a carbodiimide group, an allophanate group, a urea group, a burette group, a uretdione group, a uretoimine group, an isocyanurate group and / or an oxazolidone group is used. Urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI, etc.), urethane-modified TDI, and mixtures thereof (for example, a mixture of modified MDI and urethane-modified TDI (isocyanate-containing prepolymer)).

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

Examples of the polyurea resin (B3) include those having the diamine (b) and the diisocyanate (c) as structural units.

The vinyl resin (B4) is a polymer obtained by homopolymerizing or copolymerizing a monomer having a polymerizable double bond. Examples of the monomer having a polymerizable double bond include the following (d) to (m).

(D) Hydrocarbon having a polymerizable double bond:
(D1) Aliphatic hydrocarbon having a polymerizable double bond:
(D11) Chain hydrocarbon having a polymerizable double bond: Alkene having 2 to 30 carbon atoms (for example, ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, etc.); carbon number 4 ~ 30 alkadienes (eg butadiene, isoprene, 1,4-pentadiene, 1,5-hexadiene, 1,7-octadiene, etc.).
(D12) Cyclic hydrocarbon having a polymerizable double bond: mono or dicycloalkene having 6 to 30 carbon atoms (for example, cyclohexene, vinylcyclohexene, ethylidenebicycloheptene, etc.) and mono or dicycloalka having 5 to 30 carbon atoms Diene [for example, (di) cyclopentadiene and the like] and the like.
(D2) Aromatic hydrocarbon having a polymerizable double bond: Styrene; Hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl having 1 to 30 carbon atoms) substituted styrene (eg, α-methylstyrene, vinyl) Toluene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene, benzylstyrene, crotylbenzene, divinylbenzene, divinyltoluene, divinylxylene, trivinylbenzene, etc.); and vinylnaphthalene, etc. .

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

(F) Monomers having a sulfo group and a polymerizable double bond and their salts:
Alkene sulfonic acids having 2 to 14 carbon atoms (for example, vinyl sulfonic acid, (meth) allyl sulfonic acid and methyl vinyl sulfonic acid); styrene sulfonic acid and alkyl (2 to 24 carbon) derivatives thereof (for example, α-methyl styrene sulfone) Acid etc .; C5-C18 sulfo (hydroxy) alkyl (meth) acrylate (for example, sulfopropyl (meth) acrylate, 2-hydroxy-3- (meth) acryloxypropanesulfonic acid, 2- (meth) acryloyloxyethane) Sulfonic acid and 3- (meth) acryloyloxy-2-hydroxypropanesulfonic acid); sulfo (hydroxy) alkyl (meth) acrylamide having 5 to 18 carbon atoms [for example, 2- (meth) acryloylamino-2,2-dimethyl Ethanesulfonic acid, 2- (meth) acrylamid 2-methylpropanesulfonic acid and 3- (meth) acrylamide-2-hydroxypropanesulfonic acid, etc.]; alkyl (C3-C18) allylsulfosuccinic acid (for example, propylallylsulfosuccinic acid, butylallylsulfosuccinic acid, 2-ethylhexyl) -Allylsulfosuccinic acid, etc.]; poly [n (degree of polymerization; the same applies hereinafter) = 2-30] oxyalkylene (oxyethylene, oxypropylene, oxybutylene, etc.) Oxyalkylene may be used alone or in combination. The form may be random addition or block addition.) Mono (meth) acrylate sulfate [for example, poly (n = 5-15) oxyethylene monomethacrylate sulfate and poly (n = 5-15) oxypropylene monomethacrylate sulfate Etc.]; And compounds represented by the general formulas (1) to (3); and salts thereof.
In addition, as a salt, what was illustrated as a salt which comprises the salt of the monomer which has (e) a carboxyl group and a polymerizable double bond is mentioned.

[In the formulas (1) to (3), R ¹ is an alkylene group having 2 to 4 carbon atoms, and R ¹ O may be used alone or in combination of two or more. R ² and R ³ are each independently an alkyl group having 1 to 15 carbon atoms; m and n are each independently a number of 1 to 50; Ar is a benzene ring; R ⁴ is Represents an alkyl group having 1 to 15 carbon atoms which may be substituted with a fluorine atom. ]

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

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

(I) Nitrogen-containing monomer having a polymerizable double bond:
(I1) Monomer having amino group and polymerizable double bond:
Aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, t-butylaminoethyl methacrylate, N-aminoethyl (meth) acrylamide, (meth) allylamine, morpholinoethyl (meth) acrylate, 4-vinylpyridine, 2-vinylpyridine, crotylamine, N, N-dimethylaminostyrene, methyl-α-acetaminoacrylate, vinylimidazole, N-vinylpyrrole, N-vinylthiopyrrolidone, N-arylphenylenediamine, aminocarbazole Aminothiazole, aminoindole, aminopyrrole, aminoimidazole, aminomercaptothiazole, and salts thereof.
(I2) Monomer having an amide group and a polymerizable double bond:
(Meth) acrylamide, N-methyl (meth) acrylamide, N-butyl acrylamide, diacetone acrylamide, N-methylol (meth) acrylamide, N, N′-methylene-bis (meth) acrylamide, cinnamic amide, N, N -Dimethylacrylamide, N, N-dibenzylacrylamide, methacrylformamide, N-methyl-N-vinylacetamide, N-vinylpyrrolidone and the like.
(I3) A monomer having 3 to 10 carbon atoms having a nitrile group and a polymerizable double bond:
(Meth) acrylonitrile, cyanostyrene, cyanoacrylate and the like.
(I4) A monomer having 8 to 12 carbon atoms having a nitro group and a polymerizable double bond:
Nitrostyrene etc.

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

(K) C2-C16 monomer having a halogen element and a polymerizable double bond:
Vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride, chlorostyrene, bromostyrene, dichlorostyrene, chloromethylstyrene, tetrafluorostyrene, chloroprene and the like.

(M) An ester having a polymerizable double bond, an ether having a polymerizable double bond, a ketone having a polymerizable double bond, and a sulfur-containing compound having a polymerizable double bond:
(M1) C4-C16 ester having a polymerizable double bond:
Vinyl acetate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl methacrylate, methyl-4-vinyl benzoate, cyclohexyl methacrylate, benzyl methacrylate, phenyl (meth) acrylate, vinyl methoxyacetate, vinyl benzoate, ethyl -Α-ethoxyacrylate, alkyl (meth) acrylate having an alkyl group having 1 to 50 carbon atoms [methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl ( (Meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate and eicosyl (meth) a Relate, etc.], dialkyl fumarate (two alkyl groups are linear, branched or alicyclic groups having 2 to 8 carbon atoms), dialkyl maleate (two alkyl groups are carbon atoms 2-8 linear, branched or alicyclic groups), poly (meth) allyloxyalkanes (diallyloxyethane, triaryloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetra Monomers having a polyalkylene glycol chain and a polymerizable double bond [polyethylene glycol [Mn = 300] mono (meth) acrylate, polypropylene glycol (Mn = 500) mono), such as allyloxybutane and tetrametaallyloxyethane) Acrylate, methyl alcohol EO 10 mol adduct (meth) acrylate and lauryl alcohol EO 30 mol adduct (meth) Acrylates, etc.], poly (meth) acrylates [poly (meth) acrylates of polyhydric alcohols: ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane Tri (meth) acrylate and polyethylene glycol di (meth) acrylate, etc.].
(M2) C3-C16 ether having a polymerizable double bond:
Vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl butyl ether, vinyl-2-ethylhexyl ether, vinyl phenyl ether, vinyl-2-methoxyethyl ether, methoxybutadiene, vinyl-2-butoxyethyl ether, 3,4-dihydro -1,2-pyran, 2-butoxy-2′-vinyloxydiethyl ether, acetoxystyrene, phenoxystyrene, and the like.
(M3) C4-C12 ketone having a polymerizable double bond:
Examples include vinyl methyl ketone, vinyl ethyl ketone, and vinyl phenyl ketone.
(M-4) a sulfur-containing compound having 2 to 16 carbon atoms having a polymerizable double bond:
Examples thereof include divinyl sulfide, p-vinyl diphenyl sulfide, vinyl ethyl sulfide, vinyl ethyl sulfone, divinyl sulfone, and divinyl sulfoxide.

  As the epoxy resin (B5), a ring-opening polymer of polyepoxide (n), polyepoxide (n) and an active hydrogen-containing compound [water, diol (a21), dicarboxylic acid (a11), diamine (b), etc.] A polyadduct etc. are mentioned.

Examples of the polyepoxide (n) include aromatic polyepoxy compounds, heterocyclic polyepoxy compounds, alicyclic polyepoxy compounds, and aliphatic polyepoxy compounds.
Examples of the aromatic polyepoxy compounds include glycidyl ethers and glycidyl ethers of polyhydric phenols, glycidyl aromatic polyamines, and glycidylates of aminophenols.
Examples of glycidyl ethers of polyphenols include bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol B diglycidyl ether, bisphenol AD diglycidyl ether, bisphenol S diglycidyl ether, halogenated bisphenol A diglycidyl, and tetrachlorobisphenol A. Diglycidyl ether, catechin diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, pyrogallol triglycidyl ether, 1,5-dihydroxynaphthalene diglycidyl ether, dihydroxybiphenyl diglycidyl ether, octachloro-4,4'-dihydroxybiphenyldi Glycidyl ether, tetramethylbiphenyl diglycidyl ether Ter, dihydroxynaphthylcresol triglycidyl ether, tris (hydroxyphenyl) methane triglycidyl ether, dinaphthyltriol triglycidyl ether, tetrakis (4-hydroxyphenyl) ethanetetraglycidyl ether, p-glycidylphenyldimethyltolylbisphenol A glycidyl ether, trismethyl -T-butyl-butylhydroxymethane triglycidyl ether, 9,9'-bis (4-hydroxyphenyl) furorange glycidyl ether, 4,4'-oxybis (1,4-phenylethyl) tetracresol glycidyl ether, 4 , 4′-oxybis (1,4-phenylethyl) phenylglycidyl ether, bis (dihydroxynaphthalene) tetraglycidyl ether, phenol or By condensation reaction of glycidyl ether of cresol novolak resin, glycidyl ether of limonene phenol novolak resin, diglycidyl ether obtained from the reaction of 2 mol of bisphenol A and 3 mol of epichlorohydrin, phenol and glyoxal, glutaraldehyde or formaldehyde Examples thereof include polyglycidyl ethers of polyphenols obtained and polyglycidyl ethers of polyphenols obtained by condensation reaction of resorcin and acetone.
Examples of the glycidyl ester of polyhydric phenol include phthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, and terephthalic acid diglycidyl ester.
Examples of the glycidyl aromatic polyamine include N, N-diglycidylaniline, N, N, N ′, N′-tetraglycidylxylylenediamine and N, N, N ′, N′-tetraglycidyldiphenylmethanediamine. Furthermore, as the aromatic system, tolylene diisocyanate or a diglycidyl urethane compound obtained by addition reaction of diphenylmethane diisocyanate and glycidol, a glycidyl group-containing polyurethane (pre) polymer obtained by reacting the two reactants with a polyol, and bisphenol A The diglycidyl ether form of the AO adduct of
A triglycidyl melamine is mentioned as a heterocyclic polyepoxy compound. ; As the alicyclic polyepoxy compound, vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl) ether, ethylene glycol bisepoxy dicyclopentyl ether, 3,4-epoxy -6-methylcyclohexylmethyl-3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, bis (3,4-epoxy-6-methyl (Cyclohexylmethyl) butylamine and dimer acid diglycidyl ester. The alicyclic group also includes a nuclear hydrogenated product of the aromatic polyepoxide compound. Examples of the aliphatic polyepoxy compound include polyglycidyl ethers of polyhydric aliphatic alcohols, polyglycidyl esters of polyhydric fatty acids, and glycidyl aliphatic amines. Polyglycidyl ethers of polyhydric aliphatic alcohols include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol Examples include diglycidyl ether, polytetramethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether and polyglycerol polyglycidyl ether. It is done. Examples of polyglycidyl ester of polyvalent fatty acid include diglycidyl oxalate, diglycidyl malate, diglycidyl succinate, diglycidyl glutarate, diglycidyl adipate and diglycidyl pimelate. Examples of the glycidyl aliphatic amine include N, N, N ′, N′-tetraglycidylhexamethylenediamine. As the aliphatic group, a (co) polymer of diglycidyl ether and glycidyl (meth) acrylate is also included.
Among the polyepoxides (n), an aliphatic polyepoxy compound and an aromatic polyepoxy compound are preferable. Two or more polyepoxides may be used in combination.

The resin (B) in the present invention may be obtained from the precursor (B0).
The precursor (B0) is not particularly limited as long as it can be converted into a resin (B) by a chemical reaction. In the case of the resin (B5), (B0) includes a combination of a prepolymer (α) having a reactive group and a curing agent (β).
When (B) is a vinyl resin (B4), examples of (B0) include the monomers (d) to (m).
Among (B0), a combination of a prepolymer (α) having a reactive group and a curing agent (β) is preferable from the viewpoint of productivity.

  When a combination of a prepolymer (α) having a reactive group and a curing agent (β) is used as the precursor (B0), the “reactive group” possessed by (α) is a reaction with the curing agent (β). A possible group. In this case, examples of the method of forming (B) by reacting the precursor (B0) include a method of reacting (α) and (β) by heating to form (B).

Examples of the combination of the reactive group contained in the reactive group-containing prepolymer (α) and the curing agent (β) include the following [1] and [2].
[1] A combination in which the reactive group of (α) is a functional group (α1) capable of reacting with an active hydrogen compound, and (β) is an active hydrogen group-containing compound (β1).
[2] A combination in which the reactive group of (α) is an active hydrogen-containing group (α2), and (β) is a compound (β2) that can react with the active hydrogen-containing group.
In the combination [1], as the functional group (α1) capable of reacting with the active hydrogen compound, an isocyanate group (α1a), a blocked isocyanate group (α1b), an epoxy group (α1c), an acid anhydride group (α1d) and An acid halide group (α1e) and the like can be mentioned. Of these, (α1a), (α1b) and (α1c) are preferred, and (α1a) and (α1b) are more preferred.
The blocked isocyanate group (α1b) refers to an isocyanate group blocked with a blocking agent.
Examples of the blocking agent include oximes (acetoxime, methyl isobutyl ketoxime, diethyl ketoxime, cyclopentanone oxime, cyclohexanone oxime, methyl ethyl ketoxime, etc.); lactams (γ-butyrolactam, ε-caprolactam and γ-valerolactam) C1-20 aliphatic alcohols (ethanol, methanol, octanol, etc.); phenols (phenol, m-cresol, xylenol, nonylphenol, etc.); active methylene compounds (acetylacetone, ethyl malonate, and ethyl acetoacetate) Etc.); basic nitrogen-containing compounds (N, N-diethylhydroxylamine, 2-hydroxypyridine, pyridine N-oxide, 2-mercaptopyridine, etc.); and mixtures of two or more thereof And the like.
Of these, oximes are preferred, and methyl ethyl ketoxime is more preferred.

Examples of the structural unit of the reactive group-containing prepolymer (α) include polyether (αv), polyester (αw), epoxy resin (αx), polyurethane (αy), and polyurea (αz).
Examples of the polyether (αv) include polyethylene oxide, polypropylene oxide, and polybutylene oxide.
Examples of polyester (αw) include polyester resin (A).
Examples of the epoxy resin (αx) include addition condensates of bisphenols (such as bisphenol A, bisphenol F and bisphenol S) and epichlorohydrin.
Examples of polyurethane (αy) include polyaddition product of polyhydric alcohol (a2) and diisocyanate (c), and polyaddition product of polyester (αw) and diisocyanate (c).
Examples of polyurea (αz) include polyaddition products of diamine (b) and diisocyanate (c).

As a method of adding a reactive group to polyether (αv), polyester (αw), epoxy resin (αx), polyurethane (αy), polyurea (αz), etc.,
[1] A method of leaving a functional group of a constituent at the terminal by using one of two or more constituents in excess.
[2] A compound containing a functional group and a reactive group capable of reacting with the remaining functional group by leaving the functional group of the structural component at the terminal by excessively using one of two or more structural components How to react.
Etc.
In the method [1], a hydroxyl group-containing polyester prepolymer, a carboxyl group-containing polyester prepolymer, an acid halide group-containing polyester prepolymer, a hydroxyl group-containing epoxy resin prepolymer, an epoxy group-containing epoxy resin prepolymer, a hydroxyl group-containing polyurethane prepolymer, and An isocyanate group-containing polyurethane prepolymer or the like is obtained.
For example, in the case of a hydroxyl group-containing polyester prepolymer, the ratio of the constituent components is preferably such that the ratio of the polyol component and the polycarboxylic acid component is the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 2/1 to 1/1, more preferably 1.5 / 1 to 1/1, and particularly preferably 1.3 / 1 to 1.02 / 1. In the case of other skeleton and end group prepolymers, the ratios are the same except that the constituent components are changed.
In the method [2], an isocyanate group-containing prepolymer can be obtained by reacting the preprimer obtained in the method [1] with a polyisocyanate, and a blocked polyisocyanate can be reacted to react with a blocked isocyanate group. A prepolymer is obtained, an epoxy group-containing prepolymer is obtained by reacting a polyepoxide, and an acid anhydride group-containing prepolymer is obtained by reacting a polyacid anhydride.
The amount of the compound containing a functional group and a reactive group is, for example, when the isocyanate group-containing polyester prepolymer is obtained by reacting a hydroxyl group-containing polyester with a polyisocyanate, and the ratio of the polyisocyanate is an isocyanate group [NCO]. The equivalent ratio [NCO] / [OH] of the hydroxyl group [OH] of the hydroxyl group-containing polyester is preferably 5/1 to 1/1, more preferably 4/1 to 1.2 / 1, and particularly preferably 2. 5/1 to 1.5 / 1. In the case of prepolymers having other skeletons and terminal groups, the ratio is the same except that the constituent components are changed.

The number of reactive groups contained per molecule in the reactive group-containing prepolymer (α) is preferably 1 or more, more preferably 1.5 to 3 on average, and particularly preferably 1.8 to 2 on average. .5. By setting it in the above range, the molecular weight of the cured product obtained by reacting with the curing agent (β) is increased.
The Mn of the reactive group-containing prepolymer (α) is preferably 500 to 30,000, more preferably 1,000 to 20,000, and particularly preferably 2,000 to 10,000.
The Mw of the reactive group-containing prepolymer (α) is preferably 1,000 to 50,000, more preferably 2,000 to 40,000, and particularly preferably 4,000 to 20,000.

Examples of the active hydrogen group-containing compound (β1) include diamine (β1a), diol (β1b), dimercaptan (β1c) and water which may be blocked with a detachable compound. Among these, (β1a), (β1b) and water are preferable, (β1a) and water are more preferable, and blocked polyamines and water are particularly preferable.
Examples of (β1a) include the same as the diamine (b). Preferred as (β1a) is 4,4′-diaminodiphenylmethane, xylylenediamine, isophoronediamine, ethylenediamine, diethylenetriamine, triethylenetetramine, and mixtures thereof.

Examples of the diol (β1b) include those similar to the diol (a21), and preferred ranges thereof are also the same.
Examples of dimercaptan (β1c) include ethanedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, and the like.

If necessary, a reaction terminator (βs) can be used together with the active hydrogen group-containing compound (β1). By using a reaction terminator in combination with (β1) at a certain ratio, (B) can be adjusted to a predetermined molecular weight.
As the reaction terminator (βs), monoamine (diethylamine, dibutylamine, butylamine, laurylamine, monoethanolamine, diethanolamine, etc.); monoamine blocked (ketimine compound, etc.); monool (methanol, ethanol, isopropanol, butanol) And monophenols (such as butyl mercaptan and lauryl mercaptan); monoisocyanates (such as lauryl isocyanate and phenyl isocyanate); and monoepoxides (such as butyl glycidyl ether).

The active hydrogen-containing group (α2) of the reactive group-containing prepolymer (α) in the combination [2] includes an amino group (α2a), a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group) (α2b), a mercapto group ( α2c), a carboxyl group (α2d), and an organic group (α2e) blocked with a compound from which they can be removed. Among these, (α2a), (α2b) and (α2e) are preferable, and (α2b) is more preferable.
Examples of the organic group blocked with the compound from which the amino group can be removed include the same groups as in the case of (β1a).

  Examples of the compound (β2) capable of reacting with the active hydrogen-containing group include diisocyanate (β2a), polyepoxide (β2b), polycarboxylic acid (β2c), polyacid anhydride (β2d), and polyacid halide (β2e). . Of these, (β2a) and (β2b) are preferred, and (β2a) is more preferred.

  Examples of the diisocyanate (β2a) include those similar to the diisocyanate (c), and preferred ones are also the same.

Examples of the diepoxide (β2b) include aromatic diepoxy compounds and aliphatic diepoxy compounds.
Examples of the aromatic diepoxy compound include a glycidyl ether of polyhydric phenol, a glycidyl ester of an aromatic polycarboxylic acid, a glycidyl aromatic polyamine, and a glycidylated product of aminophenol.

Examples of glycidyl ethers of polyphenols include bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol B diglycidyl ether, bisphenol AD diglycidyl ether, bisphenol S diglycidyl ether, halogenated bisphenol A diglycidyl, and tetrachlorobisphenol A. Diglycidyl ether, catechin diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, pyrogallol triglycidyl ether, 1,5-dihydroxynaphthalene diglycidyl ether, dihydroxybiphenyl diglycidyl ether, octachloro-4,4'-dihydroxybiphenyldi Glycidyl ether, tetramethylbiphenyl diglycidyl ether Ter, dihydroxynaphthylcresol triglycidyl ether, tris (hydroxyphenyl) methane triglycidyl ether, dinaphthyltriol triglycidyl ether, tetrakis (4-hydroxyphenyl) ethanetetraglycidyl ether, p-glycidylphenyldimethyltolylbisphenol A glycidyl ether, trismethyl -T-butyl-butylhydroxymethane triglycidyl ether, 9,9'-bis (4-hydroxyphenyl) furorange glycidyl ether, 4,4'-oxybis (1,4-phenylethyl) tetracresol glycidyl ether, 4 , 4′-oxybis (1,4-phenylethyl) phenylglycidyl ether, bis (dihydroxynaphthalene) tetraglycidyl ether, phenol or Glycidyl ether of cresol novolak resin, glycidyl ether of limonenephenol novolak resin, diglycidyl ether obtained from the reaction of 2 mol of bisphenol A and 3 mol of epichlorohydrin, condensation reaction of phenol and glyoxal, glutaraldehyde, or formaldehyde And a polyglycidyl ether body of polyphenol obtained by a condensation reaction of resorcin and acetone.
Examples of the glycidyl ester of aromatic polyvalent carboxylic acid include diglycidyl phthalate, diglycidyl isophthalate, and diglycidyl terephthalate.
Examples of the glycidyl aromatic polyamine include N, N-diglycidylaniline, N, N, N ′, N′-tetraglycidylxylylenediamine and N, N, N ′, N′-tetraglycidyldiphenylmethanediamine.
Examples of the aromatic polyepoxy compound include tolylene diisocyanate or a diglycidyl urethane compound obtained by addition reaction of diphenylmethane diisocyanate and glycidol, and a glycidyl group-containing polyurethane (pre) polymer obtained by reacting the two reactants with a polyol. And diglycidyl ethers of AO adducts of bisphenol A.

Examples of the aliphatic polyepoxy compound include a chain aliphatic polyepoxy compound and a cyclic aliphatic polyepoxy compound.

Examples of chain aliphatic polyepoxy compounds include polyglycidyl ethers of polyhydric aliphatic alcohols, polyglycidyl esters of polyhydric fatty acids, and glycidyl aliphatic amines.
Polyglycidyl ethers of polyhydric aliphatic alcohols include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol Examples include diglycidyl ether, polytetramethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether and polyglycerol polyglycidyl ether. It is done.
Examples of polyglycidyl ester of polyvalent fatty acid include diglycidyl oxalate, diglycidyl malate, diglycidyl succinate, diglycidyl glutarate, diglycidyl adipate and diglycidyl pimelate.
Examples of the glycidyl aliphatic amine include N, N, N ′, N′-tetraglycidylhexamethylenediamine.
Examples of the aliphatic polyepoxy compound include a copolymer of diglycidyl ether and glycidyl (meth) acrylate.

Examples of the cycloaliphatic polyepoxy compounds include trisglycidyl melamine, vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl) ether, ethylene glycol bisepoxy dicyclopentyl ether, 3,4 -Epoxy-6-methylcyclohexylmethyl-3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, bis (3,4-epoxy-6 -Methylcyclohexylmethyl) butylamine and dimer acid diglycidyl ester.
Moreover, as a cycloaliphatic polyepoxy compound, the hydrogenated thing of the said aromatic polyepoxide compound is also mentioned.

  Examples of the dicarboxylic acid (β2c) include those similar to the dicarboxylic acid (a11), and preferred ones are also the same.

  The ratio of the curing agent (β) is the ratio of the equivalent [α] of the reactive group in the reactive group-containing prepolymer (α) to the equivalent of the active hydrogen-containing group [β] in the curing agent (β) [α. ] / [Β] is preferably 1/2 to 2/1, more preferably 1.5 / 1 to 1 / 1.5, and particularly preferably 1.2 / 1 to 1 / 1.2. . In addition, when a hardening | curing agent ((beta)) is water, water is handled as a bivalent active hydrogen compound.

The resin (B) may be a crystalline resin or an amorphous resin. From the viewpoint of low-temperature fixing, the resin (B) is preferably a resin containing a crystalline resin.
The crystalline resin in the present invention has a ratio (Tm / Ta) of a softening point of the resin (hereinafter abbreviated as Tm) to an endothermic peak temperature of heat of fusion (hereinafter abbreviated as Ta) of 1.55 or less, In differential scanning calorimetry (DSC), it means a resin having a clear endothermic peak rather than a stepwise change in endothermic amount.
On the other hand, the amorphous resin means a resin having (Tm / Ta) exceeding 1.55.
Tm and Ta can be measured by the following method.

<Tm measurement method>
Using a Koka flow tester {for example, “CFT-500D” [manufactured by Shimadzu Corporation]}, a 1 g measurement sample is heated at a heating rate of 6 ° C./min, and a load of 1.96 MPa is applied by a plunger. Is drawn from a nozzle having a diameter of 1 mm and a length of 1 mm, and a graph of “plunger lowering amount (flow value)” and “temperature” is drawn, corresponding to 1/2 of the maximum value of the plunger lowering amount. The temperature is read from the graph, and this value (temperature when half of the measurement sample flows out) is defined as Tm.
<Ta measurement method>
It is measured using a differential scanning calorimeter {for example, “DSC210” [manufactured by Seiko Instruments Inc.]}.
As a pretreatment, a sample to be measured for Ta is melted at 130 ° C., then cooled at a rate of 1.0 ° C./min from 130 ° C. to 70 ° C., and then 0.5 ° C./70° C. to 10 ° C. Lower the temperature at the rate of minutes Here, by DSC, the temperature is increased at a rate of temperature increase of 20 ° C./min and the endothermic change is measured, and a graph of “endothermic amount” and “temperature” is drawn. The endothermic peak temperature at 0 ° C. is Ta ′. When there are a plurality of peaks, the peak temperature having the largest endothermic amount is defined as Ta ′. Finally, the sample is stored at (Ta′−10) ° C. for 6 hours, and then stored at (Ta′−15) ° C. for 6 hours.
Next, the sample was cooled to 0 ° C. by DSC at a temperature decrease rate of 10 ° C./min, and then the temperature was increased at a temperature increase rate of 20 ° C./min. The temperature corresponding to the maximum peak is the endothermic peak temperature (Ta) of the heat of fusion.

The content rate of each component which comprises the resin particle (P) is as follows.
The content of the polyester resin (A) in the resin particles (P) is preferably 20 to 99.9% by weight based on the weight of (P), from the viewpoint of low-temperature fixability and wet heat storage stability, Preferably it is 40-99.5 weight%, Most preferably, it is 55-99 weight%.
The content of the resin (B) in the resin particles (P) is preferably 1 to 49% by weight, more preferably 5 to 5%, from the viewpoint of low-temperature fixability and storage stability, based on the weight of (P). It is 40% by weight, particularly preferably 10 to 30% by weight.
The total content of (A) and (B) in the resin particles (P) is preferably 50 to 100% by weight, more preferably 60 to 95% by weight, particularly preferably based on the weight of (P). 70 to 90% by weight.

The weight ratio [(A) / (B)] of the polyester resin (A) and the resin (B) is the total weight of (A) and (B) from the viewpoint of low-temperature fixability and wet heat storage stability of the toner. Based on this, it is preferably 99/1 to 60/40, more preferably 95/5 to 70/30, and particularly preferably 90/10 to 80/20.

The volume average particle diameter of the resin particles (P) is preferably 1 to 15 μm, more preferably 2 to 10 μm, particularly preferably 4 to 10 μm, and most preferably 4 to 7 μm.
The volume average particle diameter of (P) can be measured using a Coulter counter “Multisizer III” (manufactured by Beckman Coulter, Inc.).

The average circularity of the resin particles (P) is preferably 0.945 to 0.985, more preferably 0.950 to 0.980, and particularly preferably 0.955 to 0.975 μm.
The average circularity is a value obtained by optically detecting particles and dividing by the circumference of an equivalent circle having the same projected area. Specifically, it is measured using a flow type particle image analyzer “FPIA-2000” (manufactured by Sysmex).

Although there is no restriction | limiting in particular about the manufacturing method of the resin particle (P) of this invention, The solution (S) formed by melt | dissolving at least polyester resin (A) in the organic solvent (U) is disperse | distributed in a medium (M). After the step of obtaining the dispersion (DM), a method of obtaining the resin particles (P) by removing the organic solvent (U) and the medium (M) from the dispersion (DM) is preferable. In the case of this production method, (P) having a uniform volume average particle diameter can be produced.

Examples of the organic solvent (U) used in the present invention include aromatic hydrocarbon solvents (toluene, xylene, ethylbenzene, tetralin, etc.); aliphatic hydrocarbon solvents (n-hexane, n-heptane, n-decane, mineral spirit, and cyclohexane). Halogen solvents (methyl chloride, methyl bromide, methyl iodide, methylene dichloride, carbon tetrachloride, trichloroethylene, perchloroethylene, etc.); ester solvents (ethyl acetate, butyl acetate, methyl 2-hydroxyisobutyrate, methyl lactate) , Ethyl lactate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, methyl pyruvate and ethyl pyruvate); ether solvents (diethyl ether, tetrahydrofuran, dioxane, dioxolane, ethyl cellosolve, butyl cell Solve, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, etc.); ketone solvent (acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, cyclohexanone, etc.); alcohol solvent ( Methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2-ethylhexyl alcohol, benzyl alcohol, 2,2,3,3-tetrafluoropropanol, trifluoroethanol, etc.); amide solvent ( Dimethylformamide and dimethylacetamide); sulfoxide solvent (dimethylsulfoxide, etc.); heterocyclic compound solvent (N-methyl) Pyrrolidone) and a mixed solvent of two or more thereof.

Of these organic solvents (U), preferred are aliphatic hydrocarbon solvents, ester solvents, ether solvents, ketone solvents, and ketone solvents and alcohol solvents, and more preferred are n-hexane, n-heptane, n- Particularly preferred are ethyl acetate, which are decane, ethyl acetate, butyl acetate, acetone and methyl ethyl ketone.

In addition to (A), the resin (B) may be dissolved in a solution (S) obtained by dissolving at least the polyester resin (A) in the organic solvent (U).

Examples of the medium (M) used in the present invention include an aqueous medium, supercritical water, supercritical carbon dioxide, and liquid carbon dioxide. Among these, an aqueous medium is preferable.

The aqueous medium in the present invention can be used without limitation as long as it is a liquid containing water as an essential component. Water, an aqueous solution of an organic solvent, an aqueous solution of a surfactant, an aqueous solution of a synthetic polymer dispersant (h) and these Mixtures and the like can be used.
Examples of the organic solvent include esters or ester ether solvents, ether solvents, ketone solvents, alcohol solvents, amide solvents, sulfoxide solvents, heterocyclic compound solvents, and mixtures of two or more of these organic solvents (U). A solvent etc. are mentioned. When the solvent is contained, the content of the solvent is preferably 1 to 80% by weight based on the weight of the aqueous medium. The upper limit is more preferably 70% by weight, particularly preferably 30% by weight, and the lower limit is more preferably 2% by weight, particularly preferably 5% by weight.

In the present invention, the method for obtaining the dispersion (DM) by dispersing the solution (S) in the medium (M) is not particularly limited, and examples thereof include a dispersion machine and a method of dispersing by ultrasonic irradiation.

The disperser is not particularly limited as long as it is generally commercially available as an emulsifier or a disperser. For example, a batch emulsifier {“homogenizer” (manufactured by IKA), “polytron” (manufactured by Kinematica) and “ TK Auto Homo Mixer "[manufactured by Primics Co., Ltd.]}, Continuous Emulsifier {" Ebara Milder "[manufactured by Ebara Corporation]," TK Filmix "," TK Pipeline Homo Mixer "[Special Machine Chemical Industry Co., Ltd.], “Colloid Mill” [manufactured by Shinko Pantech Co., Ltd.], “Slasher”, “Trigonal Wet and Fine Crusher” [Suntech Co., Ltd.], “Capitol” (manufactured by Eurotech) And "Fine Flow Mill" [manufactured by Taiheiyo Kiko Co., Ltd.]}, high-pressure emulsifier {"Microfluidizer" [manufactured by Mizuho Industry Co., Ltd.], "Nanomizer" [S.G. Njiniaring Co., Ltd.] and "APV Gaurin" (manufactured by Gaurin Co., Ltd.)}, membrane emulsifier {"membrane emulsifier" [manufactured by Chilling Industries Co., Ltd.]}, vibration emulsifier {"Vibro mixer" Etc.}, an ultrasonic emulsifier {“ultrasonic homogenizer” (manufactured by Branson), etc.}, and the like.

In the present invention, the method for removing the organic solvent (U) from the dispersion (DM) is not particularly limited, and a known method can be applied. For example, the following [1] to [3] and a method combining these may be used. Applicable.
[1] A method of removing (U) and (M) by heating and / or depressurization in a general agitation / desolvation tank or a film evaporator.
[2] A method of removing (U) and (M) by air blowing in the liquid surface of (DM) or in the liquid.
[3] A method of diluting the dispersion (DM) with water and extracting (U) and (M) into water.

When the resin particle (P) contains a crystalline resin, the temperature at the time of heating by the method [1] is Tm or less, and when (P) contains an amorphous resin. It is preferably Tg or less, more preferably 5 ° C or less of Tm or Tg, particularly preferably 10 ° C or less of Tm or Tg, most preferably 20 ° C or less of Tm or Tg.
The pressure at which the pressure is reduced is preferably 0.05 MPa or less, more preferably −0.03 MPa or less.
The method [3] is a preferable method when the solvent (U) has solubility in water. Of the methods [1] to [3], the method [1] is preferable.

As a method for removing the medium (M) from the dispersion (DM), the following methods [1] to [3] and combinations thereof can be applied.
[1] A method of drying (DM) under reduced pressure or normal pressure.
[2] A method in which (DM) is solid-liquid separated by a centrifuge, a spatula filter and / or a filter press, water is added as necessary, and solid-liquid separation is repeated, and then the obtained solid is dried.
[3] A method in which (DM) is frozen and dried (so-called lyophilization).

In the above methods [1] and [2], the drying can be performed using known equipment such as a fluidized bed dryer, a vacuum dryer, and a circulating dryer. Moreover, it classifies using an air classifier or a sieve as needed, and it can also be set as predetermined particle size distribution.

The toner of the present invention comprises the resin particles (P) of the present invention, a colorant and a release agent.

  As the colorant, all of dyes and pigments used as toner colorants can be used. Specifically, carbon black, iron black, Sudan black SM, first yellow G, benzidine yellow, solvent yellow (21, 77, 114, etc.), pigment yellow (12, 14, 17, 83, etc.), Indian first orange, Irgasin Red, Paranitroaniline Red, Toluidine Red, Solvent Red (17, 49, 128, 5, 13, 22, and 48.2, etc.), Disper 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, La 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 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 ( Examples thereof include triacontanol and the like, fatty acids having 30 to 50 carbon atoms (e.g., triacontane carboxylic acid, etc.), esterified products of the above fatty alcohols and fatty acids, 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), polymethylene (such as Fischer-Tropsch wax such as sazol wax), fatty acid metal salts (such as calcium stearate) and fatty acid esters (behenic acid) Behenyl and the like).

The release agent may be added at the same time as mixing with the resin particles (P), pigments and other additives of the present invention, or added in advance when producing (A) and / or (B). May be. When the release agent contains an ester group, it is preferably added at the same time as mixing with the pigment and other additives, and when it does not have an ester group, (A) and / or (B) is produced. It is preferable to add in advance.

The content of each component constituting the toner of the present invention is as follows.
The content of the resin particles (P) of the present invention is preferably 30 to 97% by weight, more preferably 40 to 95% by weight, and particularly preferably 45 to 92% by weight based on the weight of the toner.
The content of the colorant is preferably 0.1 to 60% by weight, more preferably 0.2 to 55% by weight, and particularly preferably 0.5 to 50% by weight based on the weight of the toner.
The content of the release agent is preferably 0.1 to 30% by weight, more preferably 0.5 to 20% by weight, and particularly preferably 1 to 10% by weight based on the weight of the toner.

The toner of the present invention is a toner containing a resin particle (P) containing a polyester resin (A) having polycarboxylic acid (a1) and polyalcohol (a2) as structural units, a colorant, and a release agent. The weight average molecular weight of (A) is 1,000 to 8,000, the ester group concentration of (A) based on the weight of (A) is 16 to 30% by weight, and (A) is the above-mentioned After the step of obtaining a dispersion (DM) by dispersing in a medium (M) a solution (S) in which at least a polyester resin (A) is dissolved in an organic solvent (U), the toner satisfying Condition 1. It is obtained by removing the organic solvent (U) and the medium (M) from the dispersion (DM).

The toner of the present invention is a toner containing a polyester resin (A) having a polycarboxylic acid (a1) and a polyalcohol (a2) as structural units, a colorant, and a release agent. A toner having a weight average molecular weight of 1,000 to 8,000, an ester group concentration of (A) based on the weight of (A) of 16 to 30% by weight, and (A) satisfying conditional expression 1 above If so, the manufacturing method is not particularly limited.

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

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

The charge control agent may be dispersed inside the toner, may coat the toner surface, or may be dispersed inside the toner and coat the toner surface.

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 fluidizing agent may be either spherical or irregular, but is preferably spherical from the viewpoint of toner fluidity. The fluidizing agent preferably has a volume average particle size of 20 to 500 nm, and two or more types having different particle sizes may be used in combination.

The content of the charge control agent is preferably 0 to 20% by weight, more preferably 0.1 to 10% by weight, and particularly preferably 0.5 to 7.5% by weight based on the weight of the toner.
The content of the fluidizing agent is preferably 0 to 10% by weight, more preferably 0 to 5% by weight, and particularly preferably 0.1 to 4% by weight based on the weight of the toner.

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

  The volume average particle size of the toner of the present invention is preferably 1 to 15 μm, more preferably 2 to 10 μm, and particularly preferably 3 to 7 μm.

  The average circularity of the toner of the present invention is preferably 0.945 to 0.985, more preferably 0.950 to 0.980, and particularly preferably 0.955 to 0.975 μm.

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

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

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

<Production Example 1> [Synthesis of polyester resin (A-1)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling pipe and a nitrogen introduction pipe, 423 parts by weight of 1,2-propylene glycol (boiling point: 188 ° C., hereinafter simply referred to as propylene glycol) (recovered below) (26.0 parts by weight excluding 259 parts by weight), 387 parts (34.0 parts by mole) of PO2 mole adduct of bisphenol A, 392 parts by weight (66.5 parts by mole) terephthalic acid, 61 parts by weight of adipic acid ( 11.7 mol parts), 76 parts by weight (17.5 mol parts) of benzoic acid, 2.5 parts by weight of titanium diisopropoxybistriethanolamate as a polymerization catalyst, and water produced at 210 ° C. under a nitrogen stream. The mixture was reacted for 5 hours while distilling off, and then reacted for 1 hour under a reduced pressure of 0.007 to 0.026 MPa. Subsequently, it cooled to 180 degreeC, the trimellitic anhydride 29 weight part (4.3 mol part) was added, and it was made to react under a normal pressure for 1 hour, and the polyester resin (A-1) was obtained. The recovered propylene glycol was 259 parts by weight.

<Production Example 2> [Synthesis of polyester resin (A-2)]
Addition of 432 parts by weight of propylene glycol (66.0 mole parts excluding 264 parts recovered below) and 2 moles of PO in bisphenol A to a reaction vessel equipped with a stirrer, heating / cooling device, thermometer, cooling pipe and nitrogen introduction pipe 396 parts by weight (34.0 mol parts), 434 parts by weight of terephthalic acid (74.8 mol parts), 33 parts by weight of adipic acid (6.5 mol parts), 78 parts by weight of benzoic acid (18.2 mol parts) Then, 2.5 parts by weight of titanium diisopropoxybistriethanolamate is added as a polymerization catalyst, and after reacting for 5 hours while distilling off the generated water at 210 ° C. in a nitrogen stream, 0.007 to 0.026 MPa For 1 hour under reduced pressure. Subsequently, it cooled to 180 degreeC, 3 weight part (0.5 mol part) of trimellitic anhydride was added, and it was made to react under a normal pressure for 1 hour, and polyester resin (A-2) was obtained. The recovered propylene glycol was 265 parts by weight.

<Production Example 3> [Synthesis of polyester resin (A-3)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling pipe and a nitrogen introduction pipe, 432 parts by weight of propylene glycol (66.0 parts by mole excluding 265 parts by weight of the recovered part below), PO2 mole of bisphenol A 396 parts by weight of adduct (34.0 mol parts), 401 parts by weight of terephthalic acid (70.8 mol parts), 62 parts by weight of adipic acid (12.5 mol parts), 51 parts by weight of benzoic acid (12.3 mol parts) ), 2.5 parts by weight of titanium diisopropoxybistriethanolamate as a polymerization catalyst was added and reacted at 210 ° C. in a nitrogen stream for 5 hours while distilling off the generated water, and then 0.007-0. The reaction was performed for 1 hour under a reduced pressure of 026 MPa. Subsequently, it cooled to 180 degreeC, 29 weight part (4.4 mol part) of trimellitic anhydride was added, and it was made to react under a normal pressure for 1 hour, and the polyester resin (A-3) was obtained. The recovered propylene glycol was 265 parts by weight.

<Production Example 4> [Synthesis of polyester resin (A-4)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling pipe and a nitrogen introduction pipe, 394 parts by weight of propylene glycol (66.4 mole parts excluding 239 parts by weight of the recovered part below), PO3 moles of bisphenol A 417 parts by weight of adduct (33.6 moles), 430 parts by weight of terephthalic acid (77.0 moles), 20 parts by weight of benzoic acid (51.2 moles), titanium diisopropoxybistriethanolamate as a polymerization catalyst After adding 2.5 parts by weight and reacting for 5 hours while distilling off generated water at 210 ° C. in a nitrogen stream, the mixture was reacted for 1 hour under a reduced pressure of 0.007 to 0.026 MPa. Subsequently, it cooled to 180 degreeC, 17 weight part (2.6 mol part) of trimellitic anhydride was added, and it was made to react under a normal pressure for 1 hour, and the polyester resin (A-4) was obtained. The recovered propylene glycol was 239 parts by weight.

<Production Example 5> [Synthesis of polyester resin (A-5)]
Addition of 435 parts by weight of propylene glycol (62.3 parts by mole excluding the following 291 parts recovered) and PO3 moles of bisphenol A to a reaction vessel equipped with a stirrer, heating / cooling device, thermometer, cooling pipe and nitrogen introduction pipe 460 parts by weight (37.7 mol parts), 392 parts by weight of terephthalic acid (77.3 mol parts), 73 parts by weight of adipic acid (16.4 mol parts), 6.1 parts by weight of benzoic acid (1.6 mols) Part), 2.5 parts by weight of titanium diisopropoxybistriethanolamate as a polymerization catalyst was added and reacted at 210 ° C. under a nitrogen stream for 5 hours while distilling off the generated water, and then 0.007 to 0 The reaction was allowed to proceed for 1 hour under a reduced pressure of 0.026 MPa. Subsequently, it cooled to 180 degreeC, 27.3 weight part (4.7 mol part) of trimellitic anhydride was added, and it was made to react under a normal pressure for 1 hour, and the polyester resin (A-5) was obtained. The recovered propylene glycol was 291 parts by weight.

<Production Example 6> [Synthesis of polyester resin (A-6)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling pipe and a nitrogen introduction pipe, 419 parts by weight of propylene glycol (66.0 mole parts excluding 256 parts by weight of the recovered portion below), PO2 mole of bisphenol A 384 parts by weight of adduct (34.0 mol parts), 458 parts by weight of terephthalic acid (78.3 mol parts), 76 parts by weight of benzoic acid (17.7 mol parts), titanium diisopropoxybistriethanolamate as a polymerization catalyst After adding 2.5 parts by weight and reacting for 5 hours while distilling off generated water at 210 ° C. in a nitrogen stream, the mixture was reacted for 1 hour under a reduced pressure of 0.007 to 0.026 MPa. Subsequently, it cooled to 180 degreeC, the trimellitic anhydride 27.3 weight part (4.0 mol part) was added, and it was made to react under a normal pressure for 1 hour, and the polyester resin (A-6) was obtained. The recovered propylene glycol was 256 parts by weight.

<Production Example 7> [Synthesis of polyester resin (A-7)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling pipe and a nitrogen introduction pipe, 391 parts by weight of propylene glycol (66.4 mole parts excluding 237 parts by weight of the recovered part below), PO3 moles of bisphenol A 414 parts by weight of adduct (33.6 moles), 427 parts by weight of terephthalic acid (76.0 moles), 76 parts by weight of benzoic acid (18.6 moles), titanium diisopropoxybistriethanolamate as a polymerization catalyst After adding 2.5 parts by weight and reacting for 5 hours while distilling off generated water at 210 ° C. in a nitrogen stream, the mixture was reacted for 1 hour under a reduced pressure of 0.007 to 0.026 MPa. Next, the mixture was cooled to 180 ° C., 16.8 parts by weight (2.6 mol parts) of trimellitic anhydride and 14.2 parts by weight (2.8 mol parts) of phthalic anhydride were added, and the mixture was reacted for 1 hour under normal pressure. A polyester resin (A-7) was obtained. The recovered propylene glycol was 237 parts by weight.

<Production Example 8> [Synthesis of polyester resin (A-8)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling tube, and a nitrogen introduction tube, 410 parts by weight of propylene glycol (66.2 mol parts excluding 250 parts by weight of the following recovery), PO2 mol of bisphenol A Adduct 211 parts by weight (19.0 mol parts), PO3 mol adduct of bisphenol A 190 parts (14.8 mol parts), terephthalic acid 448 parts by weight (79.5 mol parts), benzoic acid 67 parts by weight (16 3 mol parts), 2.5 parts by weight of titanium diisopropoxybistriethanolamate as a polymerization catalyst was added, and the reaction was carried out for 5 hours while distilling off the generated water at 210 ° C. in a nitrogen stream. The reaction was performed for 1 hour under a reduced pressure of 007 to 0.026 MPa. Subsequently, it cooled to 180 degreeC, the trimellitic anhydride 27.3 weight part (4.2 mol part) was added, and it was made to react under a normal pressure for 1 hour, and the polyester resin (A-8) was obtained. The recovered propylene glycol was 250 parts by weight.

<Production Example 9> [Synthesis of polyester resin (A-9)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling pipe and a nitrogen introduction pipe, 315 parts by weight of propylene glycol (63.6 parts by mole excluding the following 161 parts by weight of recovery), PO2 mole of bisphenol A Adduct 404 parts by weight (19.0 moles), terephthalic acid 459 parts by weight (81.2 moles), benzoic acid 61 parts by weight (14.7 moles), titanium diisopropoxybistriethanolamate as a polymerization catalyst After adding 2.5 parts by weight and reacting for 5 hours while distilling off generated water at 210 ° C. in a nitrogen stream, the mixture was reacted for 1 hour under a reduced pressure of 0.007 to 0.026 MPa. Subsequently, it cooled to 180 degreeC, the trimellitic anhydride 27.3 weight part (4.2 mol part) was added, and it was made to react under a normal pressure for 1 hour, and polyester resin (A-9) was obtained. The recovered propylene glycol was 161 parts by weight.

<Production Example 10> [Synthesis of Polyester Resin (A-10)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling pipe and a nitrogen introduction pipe, 234 parts by weight of propylene glycol (35.4 parts by mole excluding 165 parts by weight of the following recovery part), PO2 moles of bisphenol A 571 parts by weight of adduct (64.6 parts by mole), 340 parts by weight of terephthalic acid (72.9 parts by mole), 76 parts of benzoic acid (22.1 parts by mole), titanium diisopropoxybistriethanolamate 2 as a polymerization catalyst .5 parts by weight was added and reacted for 5 hours while distilling off the water produced at 210 ° C. under a nitrogen stream, and then reacted for 1 hour under a reduced pressure of 0.007 to 0.026 MPa. Subsequently, it cooled to 180 degreeC, 27.3 weight part (5.1 mol part) of trimellitic anhydride was added, and it was made to react under a normal pressure for 1 hour, and the polyester resin (A-10) was obtained. The recovered propylene glycol was 165 parts.

<Production Example 11> [Synthesis of Polyester Resin (A-11)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling pipe and a nitrogen introduction pipe, 405 parts by weight of propylene glycol (66.0 mole parts excluding 248 parts by weight of the following recovery), PO2 mole of bisphenol A 371 parts by weight of adduct (34.0 parts by mole), 442 parts by weight of terephthalic acid (78.2 parts by weight), 107 parts by weight of t-butylbenzoic acid (17.6 parts by mole), titanium diisopropoxybistri as a polymerization catalyst After adding 2.5 parts by weight of ethanolaminate and reacting for 5 hours while distilling off generated water under a nitrogen stream at 210 ° C., the reaction was allowed to proceed for 1 hour under a reduced pressure of 0.007 to 0.026 MPa. . Subsequently, it cooled to 180 degreeC, the trimellitic anhydride 27.3 weight part (4.0 mol part) was added, and it was made to react under a normal pressure for 1 hour, and the polyester resin (A-11) was obtained. The recovered propylene glycol was 256 parts by weight.

<Production Example 12> [Synthesis of polyester resin (A-12)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling tube and a nitrogen introduction tube, 311 parts by weight of propylene glycol (65.7 mol parts excluding 144 parts by weight of the following recovery), PO2 mol of bisphenol A Adduct 393,398 parts by weight (34.3 parts by mole), terephthalic acid 452 parts by weight (81.1 parts by weight), benzoic acid 5,960 parts by weight (14.7 parts by weight), and titanium diisopropoxy as a polymerization catalyst After adding 2.5 parts by weight of bistriethanolaminate and reacting at 210 ° C. under a nitrogen stream for 5 hours while distilling off generated water, the reaction is allowed to proceed for 1 hour under a reduced pressure of 0.007 to 0.026 MPa. It was. Subsequently, it cooled to 180 degreeC, 27.3 weight part (4.2 mol part) of trimellitic anhydride was added, and it was made to react under a normal pressure for 1 hour, and polyester resin (A-12) was obtained. The recovered propylene glycol was 144 parts by weight.

<Production Example 13> [Synthesis of Polyester Resin (A-13)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling tube and a nitrogen introduction tube, 327 parts by weight of propylene glycol (62.0 mol parts excluding 178 parts by weight of the following recovery), PO2 mol of bisphenol A 420 parts by weight of adduct (38.0 moles), 477 parts by weight of terephthalic acid (87.7 moles), 32 parts of benzoic acid (8.0 moles), titanium diisopropoxybistriethanolamate 2 as a polymerization catalyst .5 parts was added and reacted for 5 hours while distilling off the generated water under a nitrogen stream at 210 ° C., and then reacted for 1 hour under a reduced pressure of 0.007 to 0.026 MPa. Subsequently, it cooled to 180 degreeC, the trimellitic anhydride 27.3 parts (4.3 mol part) was added, and it was made to react under a normal pressure for 1 hour, and the polyester resin (A-13) was obtained. The recovered propylene glycol was 178 parts by weight.

<Production Example 14> [Synthesis of polyester resin (A-14)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling tube, and a nitrogen introduction tube, 402 parts by weight of propylene glycol (66.0 mol parts excluding 246 parts by weight of the following recovery), PO2 mol of bisphenol A 368 parts by weight of adduct (34.0 moles), 439 parts by weight of terephthalic acid (78.2 moles), 103 parts by weight of naphthoic acid (17.6 moles), titanium diisopropoxybistriethanolamate as a polymerization catalyst After adding 2.5 parts by weight and reacting for 5 hours while distilling off generated water at 210 ° C. in a nitrogen stream, the mixture was reacted for 1 hour under a reduced pressure of 0.007 to 0.026 MPa. Subsequently, it cooled to 180 degreeC, 27.3 weight part (4.0 mol part) of trimellitic anhydride was added, and it was made to react under a normal pressure for 1 hour, and the polyester resin (A-14) was obtained. The recovered propylene glycol was 256 parts by weight.

<Production Example 15> [Synthesis of polyester resin (A-15)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling tube and a nitrogen introduction tube, 354 parts by weight of ethylene glycol (65.8 mol parts excluding 218 parts by weight of the following recovery), PO2 mol of bisphenol A 398 parts by weight of adduct (34.0 mol parts), 237 parts by weight of terephthalic acid (39.4 mol parts), 237 parts by weight of isophthalic acid (39.4 mol parts), 76 parts by weight of benzoic acid (17.2 mol parts) ), 2.5 parts by weight of titanium diisopropoxybistriethanolamate as a polymerization catalyst was added and reacted at 210 ° C. in a nitrogen stream for 5 hours while distilling off the generated water, and then 0.007-0. The reaction was performed for 1 hour under a reduced pressure of 026 MPa. Subsequently, it cooled to 180 degreeC, the trimellitic anhydride 27.3 weight part (3.9 mol part) was added, and it was made to react under a normal pressure for 1 hour, and the polyester resin (A-15) was obtained. The recovered ethylene glycol was 218 parts by weight.

<Production Example 16> [Synthesis of polyester resin (A-16)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling tube and a nitrogen introduction tube, 496 parts by weight of ethylene glycol (60.0 mol parts excluding 347 parts by weight of the following recovery), PO2 mol of bisphenol A 454 parts by weight (40.0 moles) of adduct, 433 parts by weight of terephthalic acid (86.6 moles), 38 parts by weight of adipic acid (8.7 moles), titanium diisopropoxybistriethanolamate as a polymerization catalyst After adding 2.5 parts by weight and reacting for 5 hours while distilling off generated water at 210 ° C. in a nitrogen stream, the mixture was reacted for 1 hour under a reduced pressure of 0.007 to 0.026 MPa. Subsequently, it cooled to 180 degreeC, the trimellitic anhydride 27.3 weight part (4.7 mol part) was added, and it was made to react under a normal pressure for 1 hour, and the polyester resin (A-16) was obtained. The recovered ethylene glycol was 347 parts by weight.

<Comparative Production Example 1> [Synthesis of Comparative Polyester Resin (RA-1)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling tube, and a nitrogen introduction tube, 503 parts by weight of propylene glycol (100.0 moles), 732 parts by weight of terephthalic acid (96.9 moles), polymerization After adding 2.5 parts by weight of titanium diisopropoxybistriethanolamate as a catalyst and reacting for 5 hours while distilling off generated water at 210 ° C. in a nitrogen stream, the pressure was reduced to 0.007 to 0.026 MPa. The reaction was allowed to proceed for 1 hour. Subsequently, it cooled to 180 degreeC, 27.3 weight part (3.1 mol part) of trimellitic anhydride was added, and it was made to react under a normal pressure for 1 hour, and polyester resin (RA-1) was obtained. The recovered propylene glycol was 106 parts by weight.

<Comparative Production Example 2> [Synthesis of Comparative Polyester Resin (RA-2)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling tube and a nitrogen introduction tube, 642 parts by weight of propylene glycol (100.0 moles), 701 parts by weight of terephthalic acid (90.1 moles), adipine 47 parts by weight (6.9 parts by mole) of acid and 2.5 parts by weight of titanium diisopropoxybistriethanolamate as a polymerization catalyst were added, and the reaction was carried out for 5 hours while distilling off the generated water at 210 ° C. in a nitrogen stream. Then, the mixture was reacted for 1 hour under a reduced pressure of 0.007 to 0.026 MPa. Subsequently, it cooled to 180 degreeC, the trimellitic anhydride 27.3 weight part (3.0 mol part) was added, and it was made to react under a normal pressure for 1 hour, and the polyester resin (RA-1) was obtained. The recovered propylene glycol was 257 parts by weight.

<Comparative Production Example 3> [Synthesis of Comparative Polyester Resin (RA-3)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling tube and a nitrogen introduction tube, 399 parts by weight of ethylene glycol (100.0 moles), 405 parts by weight of terephthalic acid (48.6 moles), isophthalic acid 405 parts by weight of acid (48.6 parts by mole) and 2.5 parts by weight of titanium diisopropoxybistriethanolamate as a polymerization catalyst were added and reacted for 5 hours while distilling off the generated water at 210 ° C. in a nitrogen stream. Then, the mixture was reacted for 1 hour under a reduced pressure of 0.007 to 0.026 MPa. Subsequently, it cooled to 180 degreeC, 27.3 weight part (2.8 mol part) of trimellitic anhydride was added, and it was made to react under a normal pressure for 1 hour, and polyester resin (RA-2) was obtained. The recovered ethylene glycol was 64 parts by weight.

The physical properties of the polyester resins (A-1) to (A-16) obtained in Production Examples 1 to 16 and the polyester resins (RA-1) to (RA-3) obtained in Comparative Production Examples 1 to 3 are shown. Table 1 shows.

<Production Examples 17 to 32, Comparative Production Examples 4 to 6> [Production of Solutions (S-1) to (S-16) and (RS-1) to (RS-3)]
Into a reaction vessel equipped with a stirrer, 50 parts by weight of polyester resins (A-1) to (A-16) and (RA-1) to (RA-3) and 50 parts by weight of ethyl acetate were added and stirred. Thus, the resin was uniformly dissolved to obtain solutions (S-1) to (S-16) and (RS-1) to (RS-3).

<Production Example 33> [Preparation of precursor (B0-1) solution]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling tube and a nitrogen introduction tube, 681 parts by weight of an EO2 molar adduct of bisphenol A, 81 parts by weight of a PO2 molar adduct of bisphenol A, 275 parts by weight of terephthalic acid Then, 7 parts by weight of adipic acid, 22 parts by weight of trimellitic anhydride and 2 parts by weight of dibutyltin oxide were added, and after dehydration reaction at normal pressure and 230 ° C. for 5 hours, the pressure was reduced to 0.01 to 0.03 MPa. And a dehydration reaction was performed for 5 hours to obtain a polyester resin.
In a pressure-resistant reaction vessel equipped with a stirrer, a heating / cooling device, and a thermometer, 350 parts by weight of a polyester resin, 50 parts by weight of isophorone diisocyanate, 600 parts by weight of ethyl acetate, and 0.5 parts by weight of ion-exchanged water are put in a sealed state. Reaction was performed at 90 ° C. for 5 hours to obtain a precursor (B0-1) solution having an isocyanate group at the molecular end. The (B0-1) solution had a urethane group concentration of 5.2% by weight and a urea group concentration of 0.3% by weight. The solid content concentration was 50% by weight.

<Production Example 34> [Synthesis of Curing Agent (β-1)]
Into a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling tube and a thermometer, 50 parts by weight of isophoronediamine and 300 parts by weight of methyl ethyl ketone were added, and the reaction was carried out at 50 ° C. for 5 hours. Curing agent (β-1)] was obtained. The total amine value of [curing agent (β-1)] was 415.

<Production Example 35> [Synthesis of Resin (B-1)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling tube and a nitrogen introduction tube, 422 parts by weight (100.0 mol parts) of 1,6-hexanediol and 692 parts by weight of sebacic acid (98.0 mols) Part), 9 parts by weight (2.0 mol parts) of benzoic 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 the water to be distilled, then the reaction is carried out for 4 hours while distilling off the water generated under a nitrogen stream while gradually raising the temperature to 220 ° C., and further reduced pressure of 0.007 to 0.026 MPa. The reaction was conducted while distilling off water, and when the acid value became 0.5 or less, the reaction product was taken out to obtain a resin (B′-1).
In another reaction vessel equipped with a stirrer, a heating / cooling device, a cooling pipe and a thermometer, 587 parts by weight of (B′-1) and 400 parts by weight of ethyl acetate were added, and the temperature was raised to 60 ° C. After stirring and dissolving for 2 hours, water was added so that the water content in the solution was 0.05% by weight. After confirming dissolution, 12.5 parts by weight of hexamethylene diisocyanate was added, the temperature was raised to 90 ° C., and the reaction was performed for 5 hours to obtain an ethyl acetate solution of resin (B-1). Subsequently, resin (B-1) was obtained by removing ethyl acetate. When (Tm / Ta) of (B-1) is measured, it is 1.15, and (B-1) is a crystalline resin.

<Production Example 36> [Synthesis of Resin (B-2)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling tube and a nitrogen introduction tube, 420 parts by weight (100.0 mol parts) of 1,6-hexanediol and 697 parts by weight of sebacic acid (98.6 mols) Part), 6 parts by weight (1.4 mol parts) of benzoic acid, and 2.5 parts by weight of titanium diisopropoxybistriethanolamate as a polymerization catalyst, heated to 180 ° C., and generated at the same temperature under a nitrogen stream The reaction is carried out for 10 hours while distilling off the water to be distilled, then the reaction is carried out for 4 hours while distilling off the water generated under a nitrogen stream while gradually raising the temperature to 220 ° C., and further reduced pressure of 0.007 to 0.026 MPa. The reaction was conducted while distilling off water, and when the acid value became 0.5 or less, the reaction product was taken out to obtain Resin (B-2). When (Tm / Ta) of (B-2) is measured, it is 1.10, and (B-2) is a crystalline resin.

<Production Example 37> [Production of resin dispersion (BD-1)]
Into a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling pipe and a thermometer, 15 parts by weight of the resin (B-1) produced in Production Example 36 and 95 parts by weight of ethyl acetate were added, and the temperature was raised to 78 ° C. with stirring. Warm, stir at the same temperature for 30 minutes, cool to 10 ° C. over 1 hour to crystallize the crystalline resin into fine particles, wet pulverize with Ultra Visco Mill (manufactured by IMEX), and resin dispersion (BD -1) was obtained. The volume average particle size of (BD-1) was 0.5 μm, and the solid content concentration was 50% by weight.

<Production Example 38> [Production of resin dispersion (BD-2)]
In Production Example 37, a resin dispersion (BD-2) was obtained in the same manner as in Production Example 37 except that 15 parts by weight of the resin (B-1) was changed to 15 parts by weight of the resin (B-2). The volume average particle size of (BD-2) was 0.5 μm, and the solid content concentration was 50% by weight.

<Production Example 39> [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, styrene 90.0 parts by weight, methacrylic acid 90.0 parts by weight, butyl acrylate 110.0 parts by weight, and ammonium persulfate 1.0 part by weight 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 1] 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 40> [Production of Colorant Dispersion]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling tube, and a nitrogen introduction tube, 557 parts by weight of propylene glycol (17.5 moles), 569 parts by weight of dimethyl terephthalate (7.0 moles) Then, 184 parts by weight (3.0 parts by mole) of adipic acid and 3 parts by weight of tetrabutoxy titanate as a condensation catalyst were added, and the reaction was performed at 180 ° C. for 8 hours while distilling off the produced methanol. Next, while gradually raising the temperature to 230 ° C., the reaction was performed for 4 hours while distilling off the produced propylene glycol and water under a nitrogen stream, and the reaction was further performed for 1 hour under a reduced pressure of 0.007 to 0.026 MPa. The recovered propylene glycol was 175 parts by weight (5.5 mole parts). Next, the mixture is cooled to 180 ° C., 121 parts by weight (1.5 mol parts) of trimellitic anhydride is added, and after 2 hours of reaction under normal pressure sealing, the reaction is continued at 220 ° C. and normal pressure until the softening point is 180 ° C. A polyester resin (Mn = 8,500) was obtained.
Into a beaker, 20 parts by weight of copper phthalocyanine, 4 parts by weight of a colorant dispersant “Solsper's 28000” [manufactured by Avicia Co., Ltd.], 20 parts by weight of the obtained polyester resin and 56 parts by weight of ethyl acetate were added and stirred uniformly. After the dispersion, copper phthalocyanine was finely dispersed by a bead mill to obtain a colorant dispersion. The volume average particle diameter measured with “LA-920” of the colorant dispersion was 0.2 μm. The solid content concentration was 50% by weight.

<Production Example 41> [Production of modified wax]
In a pressure-resistant reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer and a dropping cylinder, 454 parts by weight of xylene, low molecular weight polyethylene “Sunwax LEL-400” [softening point: 128 ° C., manufactured by Sanyo Chemical Industries, Ltd.] 150 parts by weight were added, and after nitrogen substitution, the temperature was raised to 170 ° C. with stirring. At the same temperature, 595 parts by weight of styrene, 255 parts by weight of methyl methacrylate, 34 parts by weight of di-t-butylperoxyhexahydroterephthalate, and xylene 119 A part by weight of the mixed solution was dropped over 3 hours, and the mixture was further maintained at the same temperature for 30 minutes. Subsequently, xylene was distilled off under a reduced pressure of 0.039 MPa to obtain a modified wax. The modified wax had a graft chain SP value of 10.35 (cal / cm ³ ) ^1/2 , Mn of 1,900, Mw of 5,200, and Tg of 56.9 ° C.

<Production Example 42> [Production of release agent dispersion]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling tube and a thermometer, paraffin wax “HNP-9” [Maximum heat of fusion peak temperature: 73 ° C., manufactured by Nippon Seiki Co., Ltd.] 10 parts by weight, production example 1 part by weight of the modified wax obtained in 22 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, and then cooled to 30 ° C. over 1 hour to obtain paraffin wax. Crystallization was performed in the form of fine particles, and further wet pulverized with Ultraviscomil (manufactured by IMEX) to obtain a release agent dispersion. The obtained release agent dispersion had a volume average particle size of 0.25 μm and a solid content concentration of 50% by weight.

<Production Example 43> [Production of polyester resin emulsion]
Into a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling tube and a thermometer, 100 parts by weight of the polyester resin (A-12) obtained in Production Example 12, 50 parts by weight of ethyl acetate and 10 parts by weight of isopropanol were added, After adding 380 parts by weight of ion-exchanged water with stirring at 25 ° C., after distilling off ethyl acetate and isopropanol with an evaporator, ion-exchanged water was added so that the solid content concentration was 35% by weight to obtain a polyester resin emulsion. It was. The obtained polyester resin emulsion had a volume average particle size of 120 nm.

<Production Example 44> [Production of release agent emulsion]
Paraffin wax “HNP-9” [Maximum melting heat peak temperature: 73 ° C., Nippon Seiki Co., Ltd.] 50 parts by weight, anionic surfactant “Neogen RK” [Daiichi Kogyo Seiyaku Co., Ltd.] 0. 5 parts by weight and 200 parts by weight of ion-exchanged water are heated to 95 ° C. and dispersed using a homogenizer “Ultra Tarrax T50” (manufactured by IKA). A release agent emulsion having a volume average particle size of 200 nm was obtained. The mold release agent concentration was 20%.

<Production Example 45> [Production of Colorant Emulsion]
50 parts by weight of copper phthalocyanine, 5 parts by weight of anionic surfactant “Neogen SC” (Daiichi Kogyo Seiyaku Co., Ltd.) and ion-exchanged water are mixed, and the homogenizer “Ultra Turrax T50” (manufactured by IKA) and Ultra Dispersion was performed by sonication to obtain a colorant emulsion having a volume average particle size of 150 nm. The solid content concentration was 20% by weight.

<Examples 1-16, Comparative Examples 1-3>
Using the solutions (S-1) to (S-16) and (RS-1) to (RS-3) obtained in Production Examples 17 to 32, toners were produced by the following method.
In a beaker, 120 parts by weight of ion-exchanged water, 4.33 parts by weight of [fine particle dispersion], 1 part by weight of sodium carboxymethylcellulose, 48.5% by weight aqueous solution of “doleminyl MON-7” Co., Ltd.] 22 parts by weight and 11.6 parts by weight of ethyl acetate were added and stirred to dissolve uniformly. Next, the temperature was raised to 25 ° C., and while stirring the TK auto homomixer at 10,000 rpm at the same temperature, 15.34 parts by weight of the precursor solution (B0-1), [curing agent (β-1)] 5.5 Parts by weight, 11.7 parts by weight of colorant dispersion, 7.54 parts by weight of release agent dispersion, and solutions (S-1) to (S-16), (RS-1) to (RS-3) 55.3 parts by weight of each was added and stirred for 2 minutes. Subsequently, this dispersion (DM) was transferred to a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling pipe and a thermometer, and ethyl acetate was distilled off at 30 ° C. until the concentration reached 0.5% by weight or less. An aqueous resin dispersion of toner particles was obtained. Next, it was washed, filtered, dried at 40 ° C. for 18 hours, the volatile content was 0.5% by weight or less, and the toners (T-1) to (T-16) of the present invention and the comparative toner (RT -1) to (RT-3) were obtained.

<Examples 17 and 18>
Using the solution (S-12) obtained in Production Example 28, a toner was produced by the following method.
In a beaker, 120 parts by weight of ion-exchanged water, 4.33 parts by weight of [fine particle dispersion], 1 part by weight of sodium carboxymethylcellulose, 48.5% by weight aqueous solution of “doleminyl MON-7” Co., Ltd.] 22 parts by weight and 11.6 parts by weight of ethyl acetate were added and stirred to dissolve uniformly. Next, the temperature was raised to 25 ° C., and while stirring the TK auto homomixer at 10,000 rpm at the same temperature, 15.3 parts by weight of the precursor (B0-1) solution, [curing agent (β-1)] 5.5 Parts by weight, 11.7 parts by weight of colorant dispersion, 7.54 parts by weight of release agent dispersion, and 55.3 parts by weight of solution (S-12), resin dispersions (BD-1) to (BD-2) ) Was added in an amount of 8.2 parts by weight and stirred for 2 minutes. Next, this mixed solution was transferred to a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling pipe and a thermometer, and ethyl acetate was distilled off at 30 ° C. until the concentration reached 0.5% by weight or less. An aqueous resin dispersion was obtained. Next, the product was washed, filtered, and dried at 40 ° C. for 18 hours to obtain toners (T-17) and (T-18) of the present invention with a volatile content of 0.5 wt% or less.

<Example 19>
Using the solution (S-12) obtained in Production Example 28, a toner was produced by the following method.
In a beaker, 120 parts by weight of decane, 4.33 parts by weight of [fine particle dispersion], and 48.5% by weight of an aqueous solution of “Eleminol MON-7” of sodium dodecyl diphenyl ether disulfonate [manufactured by Sanyo Chemical Industries, Ltd.] 22 parts by weight And dissolved uniformly. Next, the temperature was raised to 25 ° C., and while stirring the TK auto homomixer at 10,000 rpm at the same temperature, 15.3 parts by weight of the precursor (B0-1) solution, [curing agent (β-1)] 5.5 Part by weight, 11.7 parts by weight of the colorant dispersion, 7.54 parts by weight of the release agent dispersion and 55.3 parts by weight of the solution (S-12) were added and stirred for 2 minutes. Subsequently, this mixed liquid was transferred to a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling pipe and a thermometer, and decane was distilled off at 30 ° C. until the concentration became 0.5% by weight or less. A resin dispersion was obtained. Next, it was washed, filtered, and dried at 40 ° C. for 18 hours to obtain a toner (T-19) of the present invention with a volatile content of 0.5 wt% or less.

<Example 20>
In the experimental apparatus of FIG. 1, first, the valves V1 and V2 were closed, and carbon dioxide (purity 99.99%) was introduced into the particle recovery tank T4 from the cylinder B2 using the pump P4, and the pressure was adjusted to 14 MPa and 40 ° C. A solution tank T1 was mixed with the solution (S-12), the colorant dispersion and the release agent dispersion, and the particle dispersion tank T2 was charged with the particle dispersion.
Next, liquid carbon dioxide is introduced into the dispersion tank T3 from the liquid carbon dioxide cylinder B1 using the pump P3, adjusted to a supercritical state (9 MPa, 40 ° C.), and further the pump P2 is connected from the tank T2. The fine particle dispersion 1 was introduced.
Next, while stirring the interior of the dispersion tank T3 at 2,000 rpm, the mixture liquid of the resin solution (S-12), the colorant dispersion, and the release agent dispersion is discharged from the tank T1 using the pump P1. Introduced into T3. After the introduction, the pressure inside T3 was 14 MPa.

In addition, the weight ratio of the preparation composition to the dispersion tank T3 is as follows.
Solution (S-12) 270 parts by weight Colorant dispersion 60 parts by weight Release agent dispersion 160 parts by weight Fine particle dispersion 45 parts by weight Carbon dioxide 550 parts by weight

The weight of the introduced carbon dioxide is obtained by calculating the density of carbon dioxide from the temperature of carbon dioxide (40 ° C.) and the pressure (15 MPa) from the state equation described in the following document, and multiplying this by the volume of the dispersion tank T3. (The same applies hereinafter).
Literature: Journal of Physical and Chemical Reference data, vol. 25, P.I. 1509 to 1596 (1997, published by American Institute of Physics)

After introducing the mixed solution of the solution (S-12), the colorant dispersion and the release agent dispersion, the mixture was stirred for 1 minute to obtain a dispersion in which resin particles were dispersed in carbon dioxide in a supercritical state.
The valve V1 was then opened and the dispersion was transferred from T3 to T4 by introducing supercritical carbon dioxide into T3 and T4 using B1 to P3. During the transfer of the dispersion from T3 to T4, the opening degree of V2 was adjusted so that the pressure was kept constant. This operation was performed for 30 seconds, and V1 was closed. By this operation, the solvent was extracted from the resin dispersion transferred into T4. Further, T4 was heated to 60 ° C. and held for 15 minutes. By this operation, the fine particles in the fine particle dispersion were fixed to the surface of the resin particles formed from the resin solution, and a toner (T-20) was obtained.

Next, the pressure was maintained at 14 MPa by adjusting the opening of the pressure adjusting valve V2 while introducing carbon dioxide from the pressure cylinder B2 into the particle recovery tank T4 using the pump P4.
By this operation, carbon dioxide containing the solvent was discharged into the solvent trap tank T5, and the toner (T-20) was captured by the filter F1. The operation of introducing carbon dioxide from the pressure cylinder B2 into the particle recovery tank T4 using the pump P4 was stopped when 5 times the amount of carbon dioxide introduced into the dispersion tank T3 was introduced into the particle recovery tank T4. . At the time of this stop, the operation of replacing carbon dioxide containing the solvent with carbon dioxide not containing the solvent and capturing the toner (T-20) in the filter F1 was completed. Further, by opening the pressure adjusting valve V2 little by little and reducing the pressure inside the particle recovery tank to atmospheric pressure, a film derived from the fine particles in the fine particle dispersion was formed on the surface of the resin particles captured by the filter F1. A toner (T-20) of the present invention was obtained.

<Example 21>
Using the polyester resin (A-12) obtained in Production Example 12, a toner was produced by the following method. 35 parts by weight of polyester resin emulsion, 8 parts by weight of anionic surfactant “Neogen RK” (Daiichi Kogyo Seiyaku Co., Ltd.), 11.7 parts by weight of colorant emulsion, 7.54 parts by weight of release agent emulsion, polychlorinated A mixture of 0.16 parts by weight of aluminum and 200 parts by weight of ion-exchanged water was placed in a round stainless steel flask, adjusted to pH 3 with nitric acid, mixed and dispersed with Ultra Turrax T50, and then heated in an oil bath. The contents in the flask were heated to 48 ° C. with stirring and held at 48 ° C. for 1 hour.
Then, a mixture of 35 parts by weight of a polyester resin emulsion and 4 parts by weight of an anionic surfactant “Neogen RK” [Daiichi Kogyo Seiyaku Co., Ltd.] was added to the above mixture. After maintaining at 48 ° C for 1 hour, sodium hydroxide was added to adjust the pH to 9. Next, the temperature of the heating oil bath was raised to 90 ° C., and the core aggregates were fused and united. After stopping the stirring, the solution in the flask was rapidly cooled using a heat exchanger. The temperature lowering rate at that time was 15 ° C./min.
Next, the solution in the flask after cooling was filtered, and further washed thoroughly with ion-exchanged water to obtain a toner (T-21).

For the toners (T-1) to (T-21) and (RT-1) to (RT-3), the volume average particle diameter and particle size distribution are measured by the following methods to obtain low-temperature fixability, heat-resistant storage stability, Wet heat and heat storage stability was evaluated. The results are shown in Tables 2 and 3.

[1] Volume average particle size, particle size distribution toners (T-1) to (T-21), (RT-1) to (RT-3) are dispersed in water to give a Coulter counter “Multisizer III” (Beckman Coulter Volume average particle size and particle size distribution.
[2] Average circularity toners (T-1) to (T-21) and (RT-1) to (RT-3) are dispersed in water to obtain a flow type particle image analyzer “FPIA-2000” [Sysmex Average circularity was measured using a product manufactured by Co., Ltd.
[3] Low-temperature fixability To toners (T-1) to (T-21) and (RT-1) to (RT-3), 1.0% by weight of “Aerosil R972” [manufactured by Nippon Aerosil Co., Ltd.] Add, mix well, and evenly place this powder on the paper to 0.6 mg / cm ² (At this time, place the powder on the paper by using a printer with the heat fixing machine removed. Other methods may be used as long as the powder can be uniformly placed at the above-described weight density). When this paper is passed through a pressure roller under the conditions of a fixing speed (heating roller peripheral speed) of 213 mm / sec and a fixing pressure (pressure roller pressure) of 1 MPa, the temperature at which the cold offset occurs is measured. The lower temperature was taken as the minimum fixing temperature.
The lower the temperature at which cold offset occurs, the better the low-temperature fixability.
[4] Heat-resistant storage stability Toners (T-1) to (T-21) and (RT-1) to (RT-3) are collected in a sealed container and allowed to stand in an atmosphere of 40 ° C. for 1 day. The degree of blocking was judged visually, and the heat resistant storage stability was evaluated according to the following criteria.
[Evaluation criteria]
○: Blocking does not occur ×: Blocking occurs [5] Humidity and heat storage stability Toners (T-1) to (T-21) and (RT-1) to (RT-3) It left still for 20 hours in the atmosphere of 40 degreeC and relative humidity 80%, the degree of blocking was judged visually, and the heat-and-moisture resistant storage stability was evaluated on the following reference | standard.
[Evaluation criteria]
A: Blocking does not occur.
○: Blocking occurs, but disperses easily when force is applied.
X: Blocking occurs and does not disperse even when force is applied.

  The toner using the resin particles of the present invention is useful as an electrophotographic toner, an electrostatic recording toner, an electrostatic printing toner, and the like because it is excellent in low-temperature fixability, durability, heat-resistant storage stability, and moisture-heat storage stability. is there.

T1: Solution tank T2: Fine particle dispersion tank T3: Dispersion tank (maximum operating pressure: 20 MPa, maximum operating temperature: 100 ° C., with stirrer)
T4: Particle recovery tank (maximum operating pressure: 20 MPa, maximum operating temperature: 100 ° C.)
F1: Ceramic filter (mesh: 0.5 μm)
T5: Solvent trap B1, B2: Carbon dioxide cylinder P1, P2: Solution pump P3, P4: Carbon dioxide pump V1, V3, V4, V5, V6, V7, V8: Valve V2: Pressure adjustment valve

Claims (16)

A resin particle (P) containing a polyester resin (A) having a polycarboxylic acid (a1) and a polyhydric alcohol (a2) as structural units, and the polyester resin (A) has a weight average molecular weight of 1,000 to 8 Resin particles (P) having an ester group concentration of (A) based on the weight of (A) of 16 to 30% by weight, and (A) satisfying the following condition 1.
[Condition 1]
229 × (ECON) + 90 × (OHV) ≦ 12,000
[(ECON) represents a numerical value indicating the ester group concentration of (A) expressed in units of wt%, and (OHV) represents a numerical value indicating the hydroxyl value of (A) expressed in units of mgKOH / g. ]   The resin particles according to claim 1, wherein the resin particles (P) have a volume average particle diameter of 1 to 15 μm.   The resin particles according to claim 1 or 2, wherein the resin particles (P) have an average circularity of 0.945 to 0.985. The resin particle according to any one of claims 1 to 3, wherein the polyester resin (A) is a polyester resin further having a monocarboxylic acid (a3) and / or a monohydric alcohol (a4) as a structural unit. The acid value of the polyester resin (A) is 40 mgKOH / g or less, and the water content of (A) after storing (A) for 20 hours under the conditions of 40 ° C. and 80% relative humidity is the weight of (A). The resin particle according to any one of claims 1 to 4, wherein the resin particle is 12,000 ppm or less. After the polyester resin (A) was stored for 20 hours under the conditions of 40 ° C. and 80% relative humidity, the 1/2 drop temperature (T1) by the flow tester of (A), and 40 ° C. and relative humidity 80 of (A). %, The absolute value of the difference with the 1/2 fall temperature (T2) by the flow tester (A) before storage for 20 hours is 8 ° C. or less. The resin particles according to claim 1. The resin particle according to any one of claims 1 to 6, wherein the glass transition temperature of the polyester resin (A) is 40 to 80 ° C. The resin particle according to any one of claims 1 to 7, wherein the polyhydric alcohol (a2) contains an alkylene glycol having 2 to 10 carbon atoms. The resin particle according to any one of claims 1 to 8, wherein the monocarboxylic acid (a3) is an aromatic monocarboxylic acid (a32).   Furthermore, the resin particle in any one of Claims 1-9 containing resin (B).   The resin particle according to claim 10, wherein the resin (B) is a resin containing a crystalline resin. After the step of dispersing the solution (S) obtained by dissolving at least the polyester resin (A) in the organic solvent (U) in the medium (M) to obtain the dispersion (DM), from the dispersion (DM), The method for producing resin particles (P) according to any one of claims 1 to 11, wherein the organic solvent (U) and the medium (M) are removed. The method for producing resin particles (P) according to claim 12, wherein the medium (M) is an aqueous medium. A toner comprising the resin particles (P) according to any one of claims 1 to 11, a colorant and a release agent.   The toner according to claim 14, wherein the toner has a volume average particle diameter of 1 to 15 μm.   The toner according to claim 14, which has an average circularity of 0.945 to 0.985.

Images