Method for producing resin particles

Abstract

To provide a polyester for toner and a resin particle having excellent hot offset resistance, granulatability, and chargeability.SOLUTION: A method for producing a resin particle includes a step in which a chemical structure represented by a general formula (1) and / or (2) of a polyester resin with a number average molecular weight of 1000-10000 is combined with a metal compound in an aqueous medium. [In the general formulae (1) and (2), R1 is a hydrogen atom or an alkyl group, and R2 independently represent an alkylene group or oxyalkylene group].SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a method for producing resin particles.

Background Art

[0002] In recent years, with the development of electrophotographic systems, the demand for electrophotographic devices such as copiers and laser printers has increased rapidly, and the requirements for their performance have also become more sophisticated. Conventionally, in electrophotography, an image forming process is repeated in which a latent image based on color image information is formed on a latent image holding body such as an electrophotographic photoreceptor, the latent image is developed with toner of a corresponding color, and then the toner image is transferred onto a transfer material. After that, a method and an apparatus for obtaining a multicolor image by heat-fixing the toner image on the transfer material are known. In order to pass through these processes without problems, the toner first needs to maintain a stable charge amount (chargeability), be able to be fixed with the toner even at a low heat roll temperature (low-temperature fixability), and satisfy functions such as not fusing the toner to the heat roll even at a high fixing temperature (hot offset resistance). A polyester-based toner binder is used to exhibit low-temperature fixability, and a toner binder that can improve low-temperature fixability by introducing crystalline polyester therein has been proposed (Patent Document 1). However, in such toners, problems such as the occurrence of toner fusing to the heat roll (hot offset) are likely to occur. Also, for hot offset resistance, (1) a toner using a polyester partially crosslinked with a polyfunctional monomer as a toner binder (Patent Document 2), (2) a toner using a modified polyester resin having a crosslinked polyester resin as a skeleton and further having a reactive functional group at the end (Patent Document 3), etc. have been proposed. However, these toners have problems such that in (1), the solubility in the oil phase is low and the emulsifying property (buildability) is poor, resulting in a deteriorated particle size distribution, and in (2), the charging characteristics are deteriorated due to the positive charging property of the induced urethane group and urea group.

Prior Art Documents

Patent Document

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0004] An object of the present invention is to provide resin particles excellent in hot offset resistance, granulation property, and chargeability.

Means for Solving the Problems

[0005] As a result of intensive studies, the present inventor has reached the present invention. That is, the present invention is a method for producing resin particles having a number average molecular weight of 1000 to 10000 and including a step of bonding a chemical structure portion represented by the following general formula (1) and / or (2) of a polyester resin and a metal compound in an aqueous medium.

Chemical Formula

Advantages of the Invention

[0006] According to the present invention, it becomes possible to provide resin particles excellent in hot offset resistance, granulation property, and chargeability.

Modes for Carrying Out the Invention

[0007] The method for producing resin particles of the present invention includes a step in which a polyester resin having a number average molecular weight of 1000 to 10000 and a chemical structure portion represented by general formula (1) and / or (2) binds to a metal compound in an aqueous medium. The method for producing resin particles of the present invention will be sequentially described below.

[0008] The resin particles obtained by the present invention are resin particles containing a reaction product of a chemical structure portion represented by general formula (1) and / or (2) of a polyester resin having a chemical structure portion represented by general formula (1) and / or (2) and a metal compound. The above-mentioned reaction product refers to a resin composition obtained by coordination bonding of a chemical structure portion represented by general formula (1) and / or (2) and a metal compound.

[0009] The polyester resin in the present invention is a polyester resin characterized by having a number average molecular weight of 1000 to 10000 and a chemical structure portion represented by the following general formula (1) and / or (2). By having a structural portion represented by general formula (1) or (2), a polyester resin for toner excellent in chargeability and hot offset property can be obtained. In addition, the polyester resin in the present invention is preferably a polyester resin not containing a urethane bond and a urea bond from the viewpoint of chargeability.

[0010]

Chemical formula

[0011] The polyester resin in the present invention is not particularly limited as long as it has an average molecular weight of 1000 to 10000 and has a chemical structure part represented by the general formula (1) and / or (2). For example, a reaction product of a polyester resin having a hydroxyl group and a compound having a chemical structure part represented by the general formula (1) and / or (2) can be mentioned.

[0012] Examples of the polyester resin having a hydroxyl group include condensation type polyester polyols and polylactone polyols. The polyester having a hydroxyl group may be used alone or in combination of two or more.

[0013] The condensation type polyester polyol is not particularly limited, and examples thereof include polycondensates of polyols and polycarboxylic acids.

[0014] Examples of the polyol include diol (g) and polyol (h) having a valence of 3 or more.

[0015] Examples of the diol (g) include alkylene glycols having 2 to 36 carbon atoms, alkylene ether glycols having 4 to 36 carbon atoms, alicyclic diols having 4 to 36 carbon atoms, and aromatic diols.

[0016] Specific examples of the alkylene glycol having 2 to 36 carbon atoms include ethylene glycol, 1,2 - propylene glycol, 1,3 - propanediol, 1,4 - butanediol, 3 - methyl - 1,5 - pentanediol, 1,6 - hexanediol, octanediol, decanediol, dodecanediol, tetradecanediol, neopentyl glycol, and 2,2 - diethyl - 1,3 - propanediol.

[0017] Specific examples of the alkylene ether glycol having 4 to 36 carbon atoms include diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol.

[0018] Specific examples of the alicyclic diol having 4 to 36 carbon atoms include 1,2 - cyclohexanediol, 1,4 - cyclohexanediol, 1,1 - cyclohexanedimethanol, 1,4 - cyclohexanedimethanol, 5 - norbornene - 2,3 - dimethanol, hydrogenated bisphenol A, spiroglycol, isosorbide, and alkylene oxide (hereinafter, "alkylene oxide" may be abbreviated as AO) adducts of the above alicyclic diols.

[0019] Examples of the alkylene oxide adduct of the alicyclic diol include an ethylene oxide (hereinafter sometimes abbreviated as "EO") adduct of the alicyclic diol, a propylene oxide (hereinafter sometimes abbreviated as "PO") adduct, and a butylene oxide (hereinafter sometimes abbreviated as "BO") adduct. The average number of moles of the alkylene oxide added is preferably from 1 to 15, more preferably from 2 to 5.

[0020] Examples of the aromatic diol include 1,3-benzenedimethanol, 1,4-benzenedimethanol, bisphenol A, bisphenol F, bisphenol B, bisphenol AD, bisphenol S, trichlorobisphenol A, tetrachlorobisphenol A, dibromobisphenol F, 2-methylbisphenol A, 2,6-dimethylbisphenol A, 2,2'-diethylbisphenol F, and alkylene oxide adducts thereof.

[0021] Examples of the alkylene oxide adduct include an EO adduct, a PO adduct, and a BO adduct. The average number of moles of the alkylene oxide added is preferably from 1 to 15, more preferably from 2 to 5.

[0022] As the diol (g), in addition to the diol having no functional group other than the above hydroxyl group, a diol (g1) having another functional group may be used. Examples of (g1) include a diol having a carboxyl group, a diol having a sulfonic acid group or a sulfamic acid group, and salts thereof. Examples of the diol having a carboxyl group include dialkylolalkanoic acid. Examples of the dialkylolalkanoic acid include those having 6 to 24 carbon atoms, specifically 2,2-dimethylolpropionic acid (DMPA), 2,2-dimethylolbutanoic acid, 2,2-dimethylolheptanoic acid, 2,2-dimethyloloctanoic acid, and the like. Examples of the diol having a sulfonic acid group or a sulfamic acid group include 3-(2,3-dihydroxypropoxy)-1-propanesulfonic acid, sulfoisophthalic acid bis(ethylene glycol) ester, diol sulfamate, and bis(2-hydroxyethyl) phosphate.

[0023] Preferred diols (g) are alkylene glycols having 2 to 36 carbon atoms, aromatic diols, and diols (g1) having other functional groups, more preferably alkylene glycols having 2 to 12 carbon atoms, diols having a carboxyl group, and AO adducts of bisphenol A, and even more preferably alkylene glycols having 2 to 12 carbon atoms, AO adducts of bisphenol A, and combinations thereof.

[0024] Examples of the polyol (h) having a trivalent or higher valency include polyhydric aliphatic alcohols having 3 to 36 carbon atoms and a trivalent or higher valency, AO adducts of polyhydric aliphatic alcohols (addition mole number: 2 to 120), AO adducts of tris-phenols (such as tris-phenol PA) (addition mole number: 2 to 30), AO adducts of novolak resins (such as phenol novolak and cresol novolak) (addition mole number: 2 to 30), and acrylic polyols [such as copolymers of hydroxyethyl (meth)acrylate and other vinyl monomers]. Examples of the polyhydric aliphatic alcohols having 3 to 36 carbon atoms and a trivalent or higher valency include alkane polyols and their intramolecular or intermolecular dehydrates, and saccharides (such as sucrose) and their methyl glucosides. Specific examples of the alkane polyols and their intramolecular or intermolecular dehydrates include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, and polyglycerin.

[0025] Preferred polyols (h) having a trivalent or higher valency are polyhydric aliphatic alcohols having 3 to 36 carbon atoms and a trivalent or higher valency and AO adducts of novolak resins, and even more preferred are polyhydric aliphatic alcohols having 3 to 36 carbon atoms and a trivalent or higher valency.

[0026] Examples of the polycarboxylic acid include dicarboxylic acids (i) and polycarboxylic acids (j) having a valence of 3 or higher.

[0027] Examples of the dicarboxylic acid (i) include alkanedicarboxylic acids having 4 to 36 carbon atoms, alkenedicarboxylic acids having 4 to 36 carbon atoms, alicyclic dicarboxylic acids having 6 to 40 carbon atoms, aromatic dicarboxylic acids having 8 to 36 carbon atoms, anhydrides of these carboxylic acids, and lower alkyl (having 1 to 4 carbon atoms) esters (such as methyl esters, ethyl esters, and isopropyl esters). Examples of the alkanedicarboxylic acids having 4 to 36 carbon atoms include succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, and decylsuccinic acid. Examples of the alkenedicarboxylic acids having 4 to 36 carbon atoms include alkenylsuccinic acids such as dodecenylsuccinic acid, maleic acid, fumaric acid, citraconic acid, and mesaconic acid. Examples of the alicyclic dicarboxylic acids having 6 to 40 carbon atoms include dimer acid (dimerized linoleic acid). Examples of the aromatic dicarboxylic acids having 8 to 36 carbon atoms include phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid. Among these, preferred are alkanedicarboxylic acids having 4 to 36 carbon atoms, alkenedicarboxylic acids having 4 to 36 carbon atoms, aromatic dicarboxylic acids having 8 to 36 carbon atoms, and combinations thereof. When introducing an α,β-unsaturated carbonyl group into the polyester resin molecule, maleic acid, fumaric acid, anhydrides of these carboxylic acids, and lower alkyl (having 1 to 4 carbon atoms) esters (such as methyl esters, ethyl esters, and isopropyl esters) are preferred.

[0028] Examples of the polycarboxylic acids (j) having a valence of 3 or higher include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid), anhydrides of these carboxylic acids, and lower alkyl (having 1 to 4 carbon atoms) esters (such as methyl esters, ethyl esters, and isopropyl esters).

[0029] The reaction ratio of the polyol and the polycarboxylic acid is preferably 2 / 1 to 1.01 / 1, more preferably 1.5 / 1 to 1.01 / 1, and particularly preferably 1.2 / 1 to 1.01 / 1, as the molar ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH].

[0030] The polylactone polyol is not particularly limited, and examples thereof include, for example, the polyaddition product of lactone to diol (g), etc.

[0031] Examples of the lactone include lactones having 4 to 12 carbon atoms (for example, γ-butyrolactone, γ-valerolactone, and ε-caprolactone). Specific examples of the polylactone polyol include, for example, polycaprolactone diol, polyvalerolactone diol, and polycaprolactone triol.

[0032] The polyester having a hydroxyl group can be produced by a known production method. For example, it can be carried out by reacting a polyol and a polycarboxylic acid in an atmosphere of an inert gas (such as nitrogen gas). The reaction temperature is preferably 150 to 280 °C, and the reaction time is preferably 30 minutes or more. Also, it is effective to reduce the pressure in order to improve the reaction rate at the final stage of the reaction. At this time, an esterification catalyst can be used as needed. Examples of the esterification catalyst include tin-containing catalysts, antimony trioxide, titanium-containing catalysts, zirconium-containing catalysts, and zinc acetate. Specifically, examples of the tin-containing catalyst include dibutyltin oxide. Examples of the titanium-containing catalyst include titanium alkoxide, potassium titanyl oxalate, titanium terephthalate, the catalysts described in JP-A-2006-243715 (titanium dihydroxybis(triethanolamineate), titanium diisopropoxybistriethanolamineate, titanium monohydroxytri (triethanolamineate), and their intramolecular polycondensates, etc.) and the catalysts described in JP-A-2007-11307 (titanium tributoxyterephthalate, titanium triisopropoxyterephthalate, and titanium diisopropoxyditerephthalate, etc.). Examples of the zirconium-containing catalyst include zirconyl acetate.

[0033] Among the esterification catalysts, from the viewpoint of charging characteristics, a titanium-containing catalyst is preferable, and more preferably, the catalysts described in JP-A-2006-243715 and the catalysts described in JP-A-2007-11307.

[0034] Examples of the compound having a chemical structure portion represented by the general formula (1) and / or (2) include β-ketoester compounds and β-diester compounds, etc. One kind may be used alone, or two or more kinds may be used in combination.

[0035] Examples of the β-ketoester compound include ethyl acetoacetate, methyl acetoacetate, allyl acetoacetate, butyl acetoacetate, isopropyl acetoacetate, hexyl acetoacetate, octyl acetoacetate, decyl acetoacetate, and ethyl butyrylacetate, etc.

[0036] Examples of the β-diester compound include dimethyl malonate, diethyl malonate, dibutyl malonate, dihexyl malonate, dioctyl malonate, diundecyl malonate, dihexadecyl malonate, di-9-octadecyl malonate, di-9,12-octadecadienyl malonate, and di-9,11,13-octadecatrienyl malonate, etc.

[0037] Among the above, from the viewpoints of hot offset resistance and chargeability, β-diester compounds are preferable.

[0038] The weight ratio of the polyester resin used in the production process of the resin particles of the present invention is not particularly limited, but is preferably 5 to 30% by weight, more preferably 6 to 20% by weight, based on the weight of the resin particles.

[0039] In the polyester resin of the present invention, it is preferable that the total of the chemical structure part represented by the above general formula (1) and the chemical structure part represented by the general formula (2) is 0.10 mmol / g or more based on the weight of the polyester resin. By using the above polyester resin, a toner excellent in hot offset resistance and chargeability can be obtained. Furthermore, in the polyester resin of the present invention, it is more preferable that the total of the chemical structure part represented by the above general formula (1) and the chemical structure part represented by the general formula (2) is 0.10 to 10 mmol / g, and further preferably 0.2 to 5 mmol / g. The total number (N) mmol / g of the chemical structure part represented by the above general formula (1) of the polyester resin and the chemical structure part represented by the general formula (2) can be obtained by the following formula. N = number of moles (mol) of the compound having the chemical structure part represented by the general formula (1) or (2) / total charged weight (g) of all raw materials of the polyester resin × 1000

[0040] In the polyester resin of the present invention, it is preferable to satisfy the relationship of the following mathematical formula (1) from the viewpoints of hot offset resistance and chargeability. Number average molecular weight of the polyester resin × number of moles (mol) of the compound having the chemical structure part represented by the general formula (1) or (2) / total charged weight (g) of all raw materials of the polyester resin ≧ 0.5 (1) The left side of the above formula (1) represents the average number per molecule of the chemical structure part represented by the general formula (1) or (2) of the polyester resin. The higher this numerical value, the more the reaction points with the metal compound increase. When the reaction points with the metal compound increase, the molecular weight and crosslinking points of the reaction product of the polyester resin having the chemical structure part represented by the general formula (1) and / or (2) and the metal compound increase, so that the hot offset resistance becomes good. Further, it is more preferable to satisfy the relationship of formula (2), and it is even more preferable to satisfy the relationship of formula (3). 10 ≥ number average molecular weight of polyester resin × number of moles of compound having chemical structure part represented by general formula (1) or (2) charged (mol) / charged weight (g) of all raw materials of polyester resin ≥ 0.5 (2) 10 ≥ number average molecular weight of polyester resin × number of moles of compound having chemical structure part represented by general formula (1) or (2) charged (mol) / charged weight (g) of all raw materials of polyester resin ≥ 1 (3) The average number per molecule of the chemical structure part represented by the general formula (1) or (2) can be increased by increasing the charged amount of the raw material having the structure of (1) or (2) or increasing the molecular weight, and can be decreased by decreasing the charged amount of the raw material having the structure of (1) or (2) or decreasing the molecular weight.

[0041] The number average molecular weight (Mn) and weight average molecular weight (Mw) in the present invention can be measured under the following conditions using gel permeation chromatography (GPC). Apparatus: "HLC-8120" [manufactured by Tosoh Corporation] Columns: Two "TSK GEL GMH6" [manufactured by Tosoh Corporation] Measurement temperature: 40 °C Sample solution: 0.25 wt% tetrahydrofuran solution (insoluble matter filtered off with a glass filter) Solution injection volume: 100 μl Detector: Refractive index detector Reference substance: Standard polystyrene (TSK standard POLYSTYRENE), 12 points (molecular weights: 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]

[0042] The number average molecular weight (Mn) of the polyester resin is from 1,000 to 10,000, preferably from 1,500 to 8,000.

[0043] The weight average molecular weight (Mw) of the polyester resin is preferably from 2,000 to 50,000, more preferably from 3,000 to 30,000.

[0044] The hydroxyl value of the polyester resin is preferably from 20 to 80 mg KOH / g. The hydroxyl value can be measured by the method specified in JIS K0070.

[0045] The glass transition temperature (Tg) of the polyester resin is preferably from -70 to 80 °C, more preferably from -70 to 60 °C, and even more preferably from -50 to 50 °C. In the present invention, Tg can be measured by the method (DSC) specified in ASTM D3418-82 using "DSC20, SSC / 580" [manufactured by Seiko Instruments Inc.].

[0046] The polyester resin in the present invention can be obtained, for example, by reacting a polyester resin having a hydroxyl group with a compound having a chemical structure moiety represented by the general formula (1) and / or (2), but the reaction method is not particularly limited, and examples thereof include addition reaction, condensation reaction, transesterification reaction, etc.

[0047] The metal compound in the present invention refers to a single metal atom and its compounds, and examples thereof include alkaline earth metals such as calcium and magnesium, transition metals such as titanium, chromium, cobalt, nickel, copper, and zinc, aluminum, etc. and their compounds. From the viewpoint of the ease of coordination bonding with the polyester resin, the metal compound is preferably at least one selected from the group consisting of magnesium compounds, aluminum compounds, calcium compounds, titanium compounds, vanadium compounds, chromium compounds, manganese compounds, iron compounds, cobalt compounds, nickel compounds, copper compounds, zinc compounds, and zirconium compounds. More preferably, it is at least one selected from the group consisting of magnesium compounds, aluminum compounds, calcium compounds, and zirconium compounds. Even more preferably, it is a magnesium compound and / or an aluminum compound. Particularly preferably, it is at least one selected from the group consisting of magnesium chloride, magnesium sulfate, aluminum chloride, aluminum sulfate, polyaluminum chloride, and polyaluminum hydroxide.

[0048] The weight ratio of the metal compound used in the production process of the resin particles of the present invention is not particularly limited, but is preferably 0.05 to 10% by weight, more preferably 0.1 to 5% by weight, based on the weight of the resin particles.

[0049] In the production method of the resin particles of the present invention, the molar ratio [(S) / (T)] of the chemical structure part (S) represented by the general formula (1) and / or (2) of the polyester resin to the metal compound (T) is preferably 0.5 to 10 from the viewpoint of hot offset resistance.

[0050] Also, in the method for producing the resin particles of the present invention, in addition to the above polyester resin, metal compound, etc., other resins can be used in combination. Any known resin can be used as the other resin, and specific examples thereof include polyester resins other than the above polyester resin, vinyl resins, polyurethane resins, epoxy resins, polyamide resins, polyimide resins, silicone resins, phenolic resins, melamine resins, urea resins, aniline resins, ionomer resins, and polycarbonate resins. Preferred examples of the other resin include polyester resins other than the above polyester resin, vinyl resins, polyurethane resins, epoxy resins, and combinations thereof, and more preferably, combinations of polyester resins other than the above polyester resin and vinyl resins.

[0051] When the other resin is a polyester resin other than the above polyester resin, examples include amorphous polyester resins and crystalline polyester resins, and polycondensates using the same materials as the polyols and polycarboxylic acids exemplified by the condensation type polyester polyol can be used. Preferred examples of the polyol and polycarboxylic acid are the same as those of the above condensation type polyester polyol. In the present invention, "amorphous" means that when measuring the transition temperature of a sample using a differential scanning calorimeter, there is no peak top temperature of the endothermic peak.

[0052] When the other resin is a vinyl resin, the vinyl resin is a polymer obtained by homopolymerizing or copolymerizing vinyl monomers. Examples of the vinyl monomer include the following (1) to (10). (1) Vinyl hydrocarbons Examples of the vinyl hydrocarbon include (1-1) aliphatic vinyl hydrocarbons, (1-2) alicyclic vinyl hydrocarbons, and (1-3) aromatic vinyl hydrocarbons. (1-1) Aliphatic vinyl hydrocarbons Examples of the aliphatic vinyl hydrocarbon include alkenes and alkadienes. Specific examples of the alkene include ethylene, propylene, and α-olefins. Specific examples of the alkadiene include butadiene, isoprene, 1,4-pentadiene, 1,6-hexadiene, 1,7-octadiene, and the like. (1-2) Alicyclic vinyl hydrocarbon Examples of the alicyclic vinyl hydrocarbon include mono- or di-cycloalkene and alkadiene, and specific examples include (di)cyclopentadiene, terpene, and the like. (1-3) Aromatic vinyl hydrocarbon Examples of the aromatic vinyl hydrocarbon include styrene and its hydrocarbyl (alkyl, cycloalkyl, aralkyl, and / or alkenyl) substituted products, and specifically include α-methylstyrene, 2,4-dimethylstyrene, vinylnaphthalene, and the like.

[0053] (2) Carboxyl group-containing vinyl monomer and its salt Examples of the carboxyl group-containing vinyl monomer and its salt include unsaturated monocarboxylic acids (salts) having 3 to 30 carbon atoms, unsaturated dicarboxylic acids (salts), their anhydrides (salts), and their monoalkyl (having 1 to 24 carbon atoms) esters or their salts. Specifically, carboxyl group-containing vinyl monomers such as (meth)acrylic acid, (anhydrous) maleic acid, maleic acid monoalkyl ester, fumaric acid, fumaric acid monoalkyl ester, crotonic acid, itaconic acid, itaconic acid monoalkyl ester, itaconic acid glycol monoether, citraconic acid, citraconic acid monoalkyl ester, cinnamic acid, and metal salts thereof are included.

[0054] In the present invention, “(salt)” means an acid or its salt. For example, the unsaturated monocarboxylic acid (salt) having 3 to 30 carbon atoms means an unsaturated monocarboxylic acid or its salt.

[0055] In the present invention, “(meth)acryl” means methacrylic acid or acrylic acid. In the present invention, “(meth)acryloyl” means methacryloyl or acryloyl. In the present invention, "(meth)acrylate" means methacrylate or acrylate.

[0056] (3) Vinyl monomers containing a sulfone group, vinyl sulfate monoester compounds and salts thereof Examples of the vinyl monomers containing a sulfone group, vinyl sulfate monoester compounds and salts thereof include alkenesulfonic acids (salts) having 2 to 14 carbon atoms, alkylsulfonic acids (salts) having 2 to 24 carbon atoms, sulfo(hydroxy)alkyl-(meth)acrylate (salts) or (meth)acrylamide (salts), and alkylallylsulfosuccinic acids (salts). Specifically, examples of the alkenesulfonic acids having 2 to 14 carbon atoms include vinylsulfonic acid (salt), examples of the alkylsulfonic acids (salts) having 2 to 24 carbon atoms include α-methylstyrenesulfonic acid (salt), and examples of the sulfo(hydroxy)alkyl-(meth)acrylate (salts) or (meth)acrylamide (salts) include sulfopropyl (meth)acrylate (salt), sulfate ester (salt), or vinyl monomer (salt) containing a sulfone group.

[0057] (4) Vinyl monomers containing a phosphate group and salts thereof: Examples of the vinyl monomers containing a phosphate group and salts thereof include (meth)acryloyloxyalkyl (C1 - C24) phosphate monoesters (salts) and (meth)acryloyloxyalkyl (having 1 to 24 carbon atoms) phosphonic acids (salts). Specific examples of the (meth)acryloyloxyalkyl (C1 - C24) phosphate monoesters (salts) include 2-hydroxyethyl (meth)acryloyl phosphate (salt) and phenyl-2-acryloyloxyethyl phosphate (salt). Specific examples of the (meth)acryloyloxyalkyl (having 1 to 24 carbon atoms) phosphonic acids (salts) include 2-acryloyloxyethyl phosphonic acid (salt).

[0058] Examples of the salts in (2) to (4) above include alkali metal salts (such as sodium salts and potassium salts), alkaline earth metal salts (such as calcium salts and magnesium salts), ammonium salts, amine salts, and quaternary ammonium salts.

[0059] (5) Hydroxyl group-containing vinyl monomer Examples of the hydroxyl group-containing vinyl monomer include hydroxystyrene, N-methylol(meth)acrylamide, hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, polyethylene glycol mono(meth)acrylate, (meth)allyl alcohol, crotyl alcohol, isocrotyl alcohol, 1-butene-3-ol, 2-butene-1-ol, 2-butene-1,4-diol, propargyl alcohol, 2-hydroxyethyl propenyl ether, and sucrose allyl ether, etc.

[0060] (6) Nitrogen-containing vinyl monomer Examples of the nitrogen-containing vinyl monomer include (6-1) amino group-containing vinyl monomer, (6-2) amide group-containing vinyl monomer, (6-3) nitrile group-containing vinyl monomer, (6-4) quaternary ammonium cation group-containing vinyl monomer, and (6-5) nitro group-containing vinyl monomer, etc. (6-1) Examples of the amino group-containing vinyl monomer include aminoethyl(meth)acrylate, etc. (6-2) Examples of the amide group-containing vinyl monomer include (meth)acrylamide and N-methyl(meth)acrylamide, etc. (6-3) Examples of the nitrile group-containing vinyl monomer include (meth)acrylonitrile, cyanostyrene, and cyanoacrylate, etc. (6-4) Examples of the quaternary ammonium cation group-containing vinyl monomer include quaternized products of tertiary amine group-containing vinyl monomers such as dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylamide, diethylaminoethyl (meth)acrylamide, and diallylamine (quaternized using a quaternizing agent such as methyl chloride, dimethyl sulfate, benzyl chloride, dimethyl carbonate, etc.). (6-5) Examples of the nitro group-containing vinyl monomer include nitrostyrene.

[0061] (7) Epoxy group-containing vinyl monomer Examples of the epoxy group-containing vinyl monomer include glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, and p-vinylphenyl phenyl oxide.

[0062] (8) Halogen element-containing vinyl monomer Examples of the halogen element-containing vinyl monomer include vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride, chlorostyrene, bromostyrene, dichlorostyrene, chloromethylstyrene, tetrafluorostyrene, and chloroprene.

[0063] (9) Vinyl ester, vinyl (thio)ether, vinyl ketone (9-1) Examples of vinyl esters include vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl methacrylate, methyl 4-vinylbenzoate, cyclohexyl methacrylate, benzyl methacrylate, phenyl (meth) acrylate, vinyl methoxyacetate, vinyl benzoate, ethyl α-ethoxyacrylate, alkyl (meth) acrylates having an alkyl group with 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, octadecyl (meth) acrylate, eicosyl (meth) acrylate, behenyl (meth) acrylate, etc.], dialkyl fumarates (the two alkyl groups are linear, branched or alicyclic groups with 2 to 8 carbon atoms), dialkyl maleates (the two alkyl groups are linear, branched or alicyclic groups with 2 to 8 carbon atoms), poly (meth) allyloxyalkanes [diallyloxyethane, triallyloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, tetramethallyloxyethane, etc.], vinyl monomers having a polyalkylene glycol chain [polyethylene glycol (molecular weight 300) mono (meth) acrylate, polypropylene glycol (molecular weight 500) monoacrylate, methyl alcohol ethylene oxide 10 mol adduct (meth) acrylate, lauryl alcohol ethylene oxide 30 mol adduct (meth) acrylate, 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, polyethylene glycol di (meth) acrylate, etc.], and the like. (9-2) Examples of vinyl (thio) ethers include vinyl methyl ether and the like. (9-3) Examples of the vinyl ketone include vinyl methyl ketone and the like.

[0064] (10) Other vinyl monomers Examples of the other vinyl monomers include tetrafluoroethylene, fluoroacrylate, isocyanatoethyl (meth)acrylate, and m-isopropenyl-α,α-dimethylbenzyl isocyanate.

[0065] For the synthesis of the vinyl resin, one of the vinyl monomers (1) to (10) above may be used alone or in combination of two or more. As the vinyl resin, from the viewpoints of particle size distribution and chargeability, a styrene-(meth)acrylate copolymer and a (meth)acrylate copolymer are preferable, and a styrene-(meth)acrylate copolymer is more preferable.

[0066] In the method for producing the resin particles of the present invention, the mixing ratio of the other resin is not particularly limited, but may be 0.01 to 80% by weight, preferably 0.05 to 75% by weight, based on the weight of the resin particles. When the other resin is a polyester resin, it is preferably 50 to 80% by weight, more preferably 60 to 75% by weight, based on the weight of the resin particles. When the other resin is a vinyl resin, it is preferably 0.01 to 10% by weight, more preferably 0.05 to 2% by weight, based on the weight of the resin particles.

[0067] The resin particles of the present invention may contain various additives such as known colorants, release agents, charge control agents, fluidizing agents, etc., if necessary.

[0068] The colorant preferably contains one or more selected from the group consisting of a black colorant, a blue colorant, a red colorant, and a yellow colorant. As the colorant, all dyes, pigments, etc. used as colorants for toners can be used. Specifically, carbon black, iron black, Sudan black SM, First Yellow G, Benzidine Yellow, Solvent Yellow (such as 21, 77, and 114), Pigment Yellow (such as 12, 14, 17, and 83), Indofast Orange, Irgasin Red, Para Nitroaniline Red, Toluidine Red, Solvent Red (such as 17, 49, 128, 5, 13, 22, and 48:2), Disperse Red, Carmine FB, Pigment Orange R, Lake Red 2G, Rhodamine FB, Rhodamine B Lake, Methyl Violet B Lake, Phthalocyanine Blue, Solvent Blue (such as 25, 94, 60, and 15:3), Pigment Blue, Brilliant Green, Phthalocyanine Green, Oil Yellow GG, Kayaset YG, Orazole Brown B, and Oil Pink OP, etc. can be mentioned. Further, if necessary, magnetic powder (powders of ferromagnetic metals such as iron, cobalt, and nickel, compounds such as magnetite, hematite, and ferrite) can be contained with the function as a colorant. The content of the colorant is preferably 1 to 40 parts by weight, more preferably 2 to 15 parts by weight, based on 100 parts by weight in total of the polyester resin and other resins. When using magnetic powder, the content of the magnetic powder is preferably 20 to 150 parts by weight, more preferably 30 to 120 parts by weight, based on 100 parts by weight in total of the polyester resin and other resins.

[0069] Examples of the release agent include natural waxes (such as beeswax, carnauba wax, and montan wax), petroleum waxes (such as paraffin wax, microcrystalline wax, and petrolatum), synthetic waxes (such as Fischer-Tropsch wax, polyethylene wax, polypropylene wax, oxidized polyethylene wax, and oxidized polypropylene wax), and synthetic ester waxes (such as fatty acid esters synthesized from fatty acids having 10 to 30 carbon atoms and alcohols having 10 to 30 carbon atoms), etc. It is preferable to contain one or more selected from the group consisting of these release agents. The content of the release agent is preferably 0 to 30% by weight, more preferably 0.5 to 20% by weight, still more preferably 1 to 10% by weight, based on 100 parts by weight in total of the polyester resin and other resins.

[0070] When using the above mold release agent, a modified wax may be used in combination if necessary. The modified wax is one in which a vinyl polymer chain is grafted to the mold release agent. Examples of the mold release agent used for the modified wax are the same as those of the above mold release agent, and preferred ones are also the same. Examples of the vinyl monomer constituting the vinyl polymer chain of the modified wax include styrene and methacrylic acid ester. The vinyl polymer chain may be a homopolymer or a copolymer of the vinyl monomer. The content of the modified wax is preferably 0 to 15% by weight, more preferably 0.5 to 10% by weight, and still more preferably 1 to 5% by weight based on 100 parts by weight in total of the polyester resin and other resins.

[0071] The charge control agent may contain either a positive charge control agent or a negative charge control agent. For example, nigrosine dyes, triphenylmethane dyes containing a tertiary amine as a side chain, quaternary ammonium salts, polyamine resins, imidazole derivatives, quaternary ammonium um salt-containing polymers, metal-containing azo dyes, copper phthalocyanine dyes, metal salts of salicylic acid, boron complexes of benzoic acid, sulfonic acid group-containing polymers, fluorine-containing polymers, halogen-substituted aromatic ring-containing polymers, and the like can be mentioned. The content of the charge control agent may be 0 to 20% by weight, preferably 0.1 to 10% by weight, and more preferably 0.5 to 7.5% by weight based on 100 parts by weight in total of the polyester resin and other resins.

[0072] Examples of the fluidizing agent include silica, titania, alumina, fatty acid metal salts, silicone resin particles, and fluororesin particles, and two or more of them may be used in combination. Silica is preferred from the viewpoint of the chargeability of the toner. Further, the silica is preferably hydrophobic silica from the viewpoint of the transferability of the toner. The content of the fluidizing agent may be 0 to 10% by weight, preferably 0 to 5% by weight, and more preferably 0.1 to 4% by weight based on 100 parts by weight in total of the resin particles of the present invention.

[0073] In addition, the total weight of additives such as colorants, release agents, charge control agents, fluidizing agents, etc. may be 3 to 70% by weight, preferably 4 to 58% by weight, more preferably 5 to 50% by weight based on the weight of the resin particles.

[0074] As the aqueous medium in the present invention, any liquid containing water as an essential constituent can be used without limitation, and water, aqueous solutions of organic solvents, aqueous solutions of surfactants (s), aqueous solutions of water-soluble polymers (t), and mixtures thereof, etc. described later can be used. Examples of the method for stably forming a dispersion containing a polyester resin in an aqueous medium include a method of adding the above polyester resin to the aqueous medium and dispersing it by a shearing force. When using other resins, the above polyester resin, etc. and other resins can be mixed in advance and dispersed in an aqueous medium. Thereby, in the presence of other resins, the chemical structure part represented by the general formula (1) and / or (2) in the above polyester resin can be bonded to the metal compound. When using other resins as fine particles, the fine particles of the resin are not particularly limited as long as they can form fine particles in an aqueous medium and can adsorb to the polyester resin.

[0075] The method for producing fine particles of the resin is not particularly limited, and the following [1] to [2] can be mentioned. [1] In the case of vinyl resins, a method of directly producing a fine particle dispersion of the resin by a polymerization reaction such as suspension polymerization, emulsion polymerization, seed polymerization, and dispersion polymerization using monomers as starting materials. [2] In the case of polyaddition or condensation resins such as polyester resins, polyurethane resins, and epoxy resins, a precursor (monomers and oligomers, etc.) or a solvent solution thereof is dispersed in a medium in the presence of a suitable dispersant, and then heated or a curing agent is added to cure to produce a fine particle dispersion of the resin.

[0076] In the method of [1] or [2] above, as the emulsifier or dispersant to be used in combination, known surfactant(s), water-soluble polymer(s), etc. described below can be used. Further, an organic solvent or the like described below can be used in combination as an auxiliary agent for emulsification or dispersion.

[0077] Furthermore, when using the polyester resin of the present invention and other raw materials other than metal compounds and other resins (coloring agents, release agents, modified waxes, charge control agents, etc.), the polyester resin, etc. and other raw materials can be mixed in advance and dispersed in an aqueous medium. Also, in a state where other raw materials are mixed in advance with the polyester resin or other resins, the chemical structure part represented by the general formula (1) and / or (2) in the polyester resin can be bonded to the metal compound. Mixing and bonding other toner raw materials in the resin in advance is preferable from the viewpoints of easily dispersing and immobilizing other raw materials in the resin, particle size distribution, and chargeability. Also, in the present invention, other raw materials such as coloring agents, release agents, modified waxes, and charge control agents do not necessarily have to be mixed when forming particles in an aqueous medium, and they may be added after forming the particles. For example, after forming particles that do not contain a coloring agent, a coloring agent can also be added by a known dyeing method.

[0078] The dispersion method is not particularly limited, but known equipment such as low-speed shearing type, high-speed shearing type, friction type, high-pressure jet type, and ultrasonic can be applied. The high-speed shearing type is preferable for making the particle size of the dispersion 2 to 20 μm. When using a high-speed shearing type disperser, the rotation speed is not particularly limited, but generally it is 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The dispersion time is not particularly limited, but in the case of the batch method, it is generally 0.1 to 5 minutes. The dispersion device includes, for example, batch emulsifiers such as a homogenizer (manufactured by IKA), a Polytron (manufactured by Kinematic), a TK Auto Homomixer [manufactured by Tokushu Kika Kogyo Co., Ltd.], an Ebara milder [manufactured by Ebara Corporation], a TK Filmixer, a TK Pipeline Homomixer [manufactured by Tokushu Kika Kogyo Co., Ltd.], a colloid mill [manufactured by Shinko Pantec Co., Ltd.], an Ultraviscomill (manufactured by Aimex), a slasher, a trigonal wet fine grinder [manufactured by Mitsui Miike Kakoki Co., Ltd.], a Capitron (manufactured by Eurotech), a Fine Flow Mill [manufactured by Taiheiyo Kiko Co., Ltd.], etc., continuous emulsifiers, high-pressure emulsifiers such as a Microfluidizer [manufactured by Mizuhara Kogyo Co., Ltd.], a Nanomizer (manufactured by Nanomizer Co., Ltd.), an APV Gaulin (manufactured by Gaulin), etc., membrane emulsifiers such as a membrane emulsifier [manufactured by Reika Kogyo Co., Ltd.], vibration emulsifiers such as a Vibro Mixer [manufactured by Reika Kogyo Co., Ltd.], ultrasonic emulsifiers such as an ultrasonic homogenizer (manufactured by Branson), etc. Among these, from the viewpoint of particle size uniformity, APV Gaulin, a homogenizer, a TK Auto Homomixer, an Ebara milder, a TK Filmixer, and a TK Pipeline Homomixer are preferable.

[0079] The bonding between the chemical structure moiety represented by the general formula (1) and / or (2) and the metal compound in the polyester resin can be carried out by a known method as long as it includes a step of bonding in an aqueous medium. However, a method in which the above polyester resin is dispersed in an aqueous medium and the metal compound is dissolved and bonded in the aqueous medium after the formation of the polyester resin particles is preferable. From the viewpoint of hot offset resistance, the reaction temperature is preferably 5 to 200 °C, more preferably 10 to 100 °C, and even more preferably 15 to 60 °C. The reaction time is preferably 1 to 48 hours, and more preferably 2 to 24 hours. The reaction is carried out by heating after dispersion, but it may also be partially advanced before dispersion.

[0080] When dispersing the polyester resin of the present invention or the like in an aqueous medium, it is preferable that the polyester resin or the like is in a liquid state. When the polyester resin or the like is solid at room temperature, it may be dispersed in a liquid state at a high temperature above the melting point, or an organic solvent solution of the polyester resin or the like may be used. Using an organic solvent is preferable in that the particle size distribution becomes sharper.

[0081] Examples of the organic solvent include aromatic hydrocarbon solvents, aliphatic or alicyclic hydrocarbon solvents, halogen solvents, ester or ester-ether solvents, ether solvents, ketone solvents, alcohol solvents, amide solvents, sulfoxide solvents, heterocyclic compound solvents, and mixed solvents of two or more of these. Specific examples of the organic solvent include aromatic hydrocarbon solvents (such as toluene, xylene, ethylbenzene, and tetralin); aliphatic or alicyclic hydrocarbon solvents (such as n-hexane, n-heptane, mineral spirit, and cyclohexane); halogen solvents such as methyl chloride, methyl bromide, methyl iodide, methylene dichloride, carbon tetrachloride, trichloroethylene, and perchloroethylene; ester or ester-ether solvents such as ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, and ethyl cellosolve acetate; ether solvents such as diethyl ether, tetrahydrofuran, dioxane, ethyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, and cyclohexanone; alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2-ethylhexyl alcohol, and benzyl alcohol; amide solvents such as dimethylformamide and dimethylacetamide; sulfoxide solvents such as dimethyl sulfoxide, heterocyclic compound solvents such as N-methylpyrrolidone, and mixed solvents of two or more of these. Among the above organic solvents, volatile ones with a boiling point of less than 100 °C are preferred. Preferred organic solvents include ethyl acetate, acetone, and methyl ethyl ketone.

[0082] When dispersing the polyester resin or the like in the present invention in an aqueous medium, known surfactant(s) can be used as the emulsifier or dispersant used in combination. Using the surfactant(s) is preferred in that the volume average particle diameter of the resin particles tends to be small.

[0083] The surfactant(s) is not particularly limited, and examples thereof include anionic surfactant(s-1), cationic surfactant(s-2), amphoteric surfactant(s-3), nonionic surfactant(s-4), etc. The surfactant(s) may be a combination of two or more surfactants.

[0084] Examples of the anionic surfactant(s-1) include carboxylic acids or their salts, sulfate esters, salts of carboxymethylated products, sulfonates, and phosphate esters. Examples of the cationic surfactant(s-2) include quaternary ammonium salt type surfactants and amine salt type surfactants. Examples of the amphoteric surfactant(s-3) include carboxylate type amphoteric surfactants, sulfate ester salt type amphoteric surfactants, sulfonate type amphoteric surfactants, and phosphate ester salt type amphoteric surfactants. Examples of the nonionic surfactant(s-4) include AO addition type nonionic surfactants and polyhydric alcohol type nonionic surfactants. Specific examples of these surfactants(s) include those described in JP-A-2002-284881.

[0085] The amount of the surfactant(s) used relative to 100 parts by weight of water as the aqueous medium is preferably 0 to 300 parts by weight, more preferably 0.001 to 10 parts by weight, and particularly preferably 0.01 to 5 parts by weight.

[0086] When dispersing the polyester resin etc. in the present invention in an aqueous medium, a known water-soluble polymer(t) can be used as the emulsifier or dispersant used in combination. Using the water-soluble polymer(t) is preferable in that the volume average particle diameter of the resin particles becomes smaller and the particle size distribution (volume average particle diameter / number average particle diameter) tends to be smaller.

[0087] Examples of the water-soluble polymer (t) include cellulose compounds (such as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose, and saponified products thereof), gelatin, starch, dextrin, gum arabic, chitin, chitosan, polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, polyethyleneimine, polyacrylamide, polymers containing acrylic acid (salt) (such as sodium polyacrylate, potassium polyacrylate, ammonium polyacrylate, sodium hydroxide partially neutralized product of polyacrylic acid, and copolymer of sodium acrylate - acrylic acid ester, etc.), sodium hydroxide (partial) neutralized product of styrene - maleic anhydride copolymer, water-soluble polyurethane (reaction product of polyethylene glycol, polycaprolactone diol, etc. and polyisocyanate, etc.).

[0088] The amount of the water-soluble polymer (t) used per 100 parts by weight of water as the aqueous medium is preferably 0 to 5 parts by weight.

[0089] The resin particles obtained by the production method of the present invention are raw materials for toner which are fixed on a support (such as paper, polyester film, etc.) by a copying machine, a printer, etc. to be used as a recording material. As a method for fixing on the support, known heat roll fixing methods, flash fixing methods, etc. can be applied.

[0090] The resin particles obtained by the production method of the present invention are used for toner for developing an electrostatic charge image or a magnetic latent image in electrophotography, electrostatic recording method, electrostatic printing method, etc. More specifically, it relates to toner used for developing an electrostatic charge image or a magnetic latent image which is particularly suitable for full color.

Examples

[0091] Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto. In the following, "parts" means "parts by weight".

[0092] <Production Example 1> [Production of polyester resin (A-1)] Into a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, 439 parts of a bisphenol A·PO 2 -mol adduct, 329 parts of a bisphenol A·PO 3 -mol adduct, 56 parts of terephthalic acid, 90 parts of adipic acid, and 0.6 part of titanium diisopropoxybis(triethanolamine)ate as a condensation catalyst were charged. While gradually raising the temperature to 230°C, the reaction was carried out under a reduced pressure of 0.5 to 2.5 kPa for 10 hours. It was confirmed that the acid value was less than 1 mgKOH / g, and a polyester having a hydroxyl group was obtained. Thereafter, 100 parts of diethyl malonate was added, and the reaction was carried out at 150°C for 3 hours. Then, by-products were distilled off under a reduced pressure of 0.5 to 2.5 kPa to obtain a polyester resin (A-1).

[0093] <Production Examples 2 to 7> [Production of Polyester Resins (A-2) to (A-7)] Into a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, the alcohol component and carboxylic acid component described in Table 1 and a compound having the structure of the general formula (1) or (2) were charged, and the reaction was carried out in the same manner as in Production Example 1 to obtain polyester resins (A-2) to (A-7).

[0094] <Comparative Production Example 1> [Production of Polyester Resin (A'-1)] Into a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, 884 parts of a bisphenol A·PO 2 -mol adduct, 196 parts of terephthalic acid, and 0.6 part of titanium diisopropoxybis(triethanolamine)ate as a condensation catalyst were charged. While gradually raising the temperature to 230°C, the reaction was carried out under a reduced pressure of 0.5 to 2.5 kPa for 10 hours. It was confirmed that the acid value was less than 1 mgKOH / g, and a polyester having a hydroxyl group was obtained. Thereafter, 250 parts of ethyl acetoacetate was added, and the reaction was carried out at 150°C for 3 hours. Then, by-products were distilled off under a reduced pressure of 0.5 to 2.5 kPa to obtain a polyester resin (A'-1).

[0095] <Comparative Production Example 2> [Production of Polyester Resin (A'-2)] Into a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen inlet pipe, the alcohol component, carboxylic acid component, and compound having the structure of general formula (1) or (2) described in Table 1 were charged, and the reaction was carried out in the same manner as in Comparative Production Example 1 except for that, to obtain a polyester resin (A'-2).

[0096] <Comparative Production Example 3> [Production of Polyester Resin (A'-3)] Into a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen inlet pipe, 508 parts of 3-methyl-1,5-pentanediol, 283 parts of terephthalic acid, 249 parts of adipic acid, and 0.6 part of titanium diisopropoxybis(triethanolamineate) as a condensation catalyst were placed, and the temperature was gradually raised to 230 °C while reacting under a reduced pressure of 0.5 to 2.5 kPa for 10 hours. It was confirmed that the acid value was less than 1 mgKOH / g to obtain a polyester having a hydroxyl group. 1000 parts of the obtained polyester, 116 parts of isophorone diisocyanate (IPDI), and 884 parts of ethyl acetate were charged into an autoclave, and the reaction was carried out at 80 °C for 10 hours in a sealed state to obtain a solution of a polyester resin (A'-3) containing an isocyanate group at the molecular terminal.

[0097] The compositions and glass transition temperatures (Tg), number average molecular weights (Mn), and the left side of formula (1) of polyester resins (A-1) to (A-7), (A'-1) to (A'-3) were described in Table 1.

[0098]

Table 1

[0099] <Production Example 8> [Production of Fine Particle Dispersion] Into a reaction vessel equipped with a stirrer and a thermometer, 690.0 parts by weight of water, 9.0 parts by weight of sodium polyoxyethylene monomethacrylate sulfate "Eremol RS-30" [manufactured by Sanyo Chemical Industries, Ltd.], 90.0 parts by weight of styrene, 90.0 parts by weight of methacrylic acid, 110.0 parts by weight of butyl acrylate, and 1.0 part by weight of ammonium persulfate were charged and stirred at 350 revolutions per minute for 15 minutes, and a white emulsion was obtained. Then, the temperature was raised to 75°C and reacted at the same temperature for 5 hours. Further, 30 parts by weight of a 1% by weight aqueous ammonium persulfate solution was added and aged at 75°C for 5 hours to obtain a fine particle dispersion of a vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-sodium salt of ethylene oxide adduct sulfate of methacrylic acid). When the volume average particle diameter of the particles dispersed in the fine particle dispersion was measured using a laser diffraction / scattering particle size distribution measuring device "LA-920" [manufactured by Horiba, Ltd.], it was 0.1 μm.

[0100] <Production Example 9> [Production of Colorant Dispersion Liquid] Into a reaction vessel equipped with a stirring device, a heating and cooling device, a thermometer, a cooling tube, and a nitrogen introduction tube, 557 parts of propylene glycol, 569 parts of dimethyl terephthalate, 184 parts of adipic acid, and 3 parts of tetrabutoxytitanate as a condensation catalyst were charged and reacted at 180°C under a nitrogen stream for 8 hours while distilling off the generated methanol. Then, while gradually raising the temperature to 230°C, it was reacted for 4 hours under a nitrogen stream while distilling off the generated propylene glycol and water, and further reacted for 1 hour under a reduced pressure of 0.007 to 0.026 MPa. The recovered propylene glycol was 175 parts. Then, it was cooled to 180°C, 121 parts of trimellitic anhydride was added, reacted for 2 hours under normal pressure and sealed, and then reacted at 220°C and normal pressure until the softening point reached 180°C to obtain a polyester (Mn = 8,500). Into a beaker, 20 parts of copper phthalocyanine, 4 parts by weight of a colorant dispersant "Solsperse 28000" [manufactured by Avecia Co., Ltd.], 20 parts of the obtained polyester, and 56 parts of ethyl acetate were charged, stirred and uniformly dispersed, and then copper phthalocyanine was finely dispersed by a bead mill to obtain a colorant dispersion liquid.

[0101] <Production Example 10> [Production of Modified Wax] Into a pressure-resistant reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, and a dropping funnel, 454 parts of xylene and 150 parts of low molecular weight polyethylene wax "Sun Wax LEL-400" [softening point: 128°C, manufactured by Sanyo Chemical Industries, Ltd.] were charged. After nitrogen substitution, the temperature was raised to 170°C with stirring, and a mixed solution of 595 parts of styrene, 255 parts of methyl methacrylate, 34 parts of di-t-butylperoxyhexahydroterephthalate, and 119 parts of xylene was added dropwise over 3 hours at the same temperature, and then held at the same temperature for 30 minutes. Next, xylene was distilled off under a reduced pressure of 0.039 MPa to obtain a modified wax.

[0102] <Production Example 11> [Production of Release Agent Dispersion] Into a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling pipe, and a thermometer, 10 parts of paraffin wax "HNP-9" [maximum melting heat peak temperature: 73°C, manufactured by Nippon Seiro Co., Ltd.], 1 part of the modified wax obtained in Production Example 10, and 33 parts of ethyl acetate were charged. The temperature was raised to 78°C with stirring, stirred at the same temperature for 30 minutes, then cooled to 30°C over 1 hour to crystallize the paraffin wax into fine particles, and further wet-milled with an Ultraviscomill (manufactured by Imex) to obtain a release agent dispersion.

[0103] <Production Example 12> [Production of Amorphous Polyester Resin] In a reaction tank equipped with a cooling pipe, a stirrer, and a nitrogen inlet pipe, 260 parts of bisphenol A·PO 2-mole adduct, 195 parts of bisphenol A·PO 3-mole adduct, 260 parts of bisphenol A·EO 2-mole adduct, 10 parts of trimethylolpropane, 255 parts of terephthalic acid, 45 parts of adipic acid, 0.6 part of titanium diisopropoxybistriethanolamineate as a condensation catalyst were charged. The reaction was carried out at 220°C under a nitrogen stream while distilling off the water generated until the acid value reached 20 or less, and then reacted under a reduced pressure of 0.5 - 2.5 kPa for 10 hours. Next, 30 parts by weight of trimellitic anhydride was added and held at 175°C for 1 hour to obtain an amorphous polyester resin.

[0104] <Example 1> [Production of Resin Particles (D-1)] Into a beaker, 135 parts of ion-exchanged water, 0.5 part of [fine particle dispersion], 5 parts by weight of sodium carboxymethyl cellulose, 34 parts of a 48.5 wt% aqueous solution of sodium dodecyldiphenyl ether disulfonic acid "Ereminol MON-7" [manufactured by Sanyo Chemical Industries, Ltd.] and 15 parts of ethyl acetate were charged and stirred to dissolve uniformly. Next, 9 parts of polyester resin (A-1), 40 parts of [colorant dispersion], 40 parts of [release agent dispersion], 71 parts of [amorphous polyester resin] and 54 parts of ethyl acetate were charged and stirred at 10,000 rpm for 2 minutes using a TK autohomomixer. Next, this mixed solution was transferred to a reaction vessel equipped with a stirrer and a thermometer, and ethyl acetate was distilled off at 50°C until the concentration became 0.5 wt% or less to obtain an aqueous resin dispersion of resin particles. Next, 0.5 part of aluminum sulfate was added to the obtained aqueous dispersion, stirred at room temperature for 3 hours for reaction, then washed, filtered off, and dried at 40°C for 18 hours to make the volatile content 0.5 wt% or less, thereby obtaining the resin particles (D-1) of the present invention.

[0105] <Examples 2 to 9>[Resin particles (D-2) to (D-9)] In Example 1, resin particles (D-2) were obtained in the same manner as in Example 1 except that the polyester resin (A-1) was changed to each polyester resin (A) described in Table 2 and aluminum sulfate was changed to each metal compound.

[0106] <Comparative Example 1>[Production of resin particles (D'-1)] In Example 1, resin particles (D'-1) were obtained in the same manner as in Example 1 except that the polyester resin (A-1) was changed to (A'-1).

[0107] <Comparative Example 2>[Production of resin particles (D'-2)] In Example 1, resin particles (D'-2) were obtained in the same manner as in Example 1 except that the polyester resin (A-1) was changed to (A'-2).

[0108] <Comparative Example 3>[Production of resin particles (D'-3)] Into a beaker, 135 parts of ion-exchanged water, 0.5 part of [fine particle dispersion], 5 parts by weight of sodium carboxymethyl cellulose, 34 parts of a 48.5 wt% aqueous solution of sodium dodecyl diphenyl ether disulfonate "Eleminol MON-7" [manufactured by Sanyo Chemical Industries, Ltd.] and 15 parts of ethyl acetate were charged and stirred to dissolve uniformly. Next, 18 parts of a polyester resin (A'-3) solution, 40 parts of [colorant dispersion], 40 parts of [release agent dispersion], 71 parts of [amorphous resin], 45 parts of ethyl acetate and 0.13 part of isophoronediamine were charged and stirred at 10,000 rpm for 2 minutes using a TK autohomomixer. Next, this mixture was transferred to a reaction vessel equipped with a stirrer and a thermometer, and ethyl acetate was distilled off at 50°C until the concentration became 0.5 wt% or less to obtain an aqueous resin dispersion of resin particles. Next, the obtained aqueous dispersion was washed, filtered off, and dried at 40°C for 18 hours to make the volatile content 0.5 wt% or less, thereby obtaining the resin particles (D'-3) of the present invention.

[0109] To 100 parts of resin particles (D-1) to (D-9) and (D'-1) to (D'-3), 1 part of hydrophobic silica "Aerosil R972" [manufactured by Nippon Aerosil] as a fluidizing agent was mixed using a sample mill, and the anti-hot offset property, granulation property, and chargeability were evaluated by the following method. The evaluation results are shown in Table 2.

[0110]

Table 2

[0111] [Evaluation method] The measurement methods and evaluation methods for the anti-hot offset property, granulation property, and chargeability, including the judgment criteria, are described below.

[0112] <Anti-hot offset property (hot offset generation temperature)> The resin particles after the external addition treatment are uniformly placed on the paper surface so as to be 0.8 mg / cm 2 At this time, as a method of placing the powder on the paper surface, a printer with the heat fixing unit removed is used. Other methods may be used as long as the powder can be uniformly placed at the above weight density. This paper was 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 10 kg / cm 2 and the generation temperature of hot offset was measured. Generally, under these evaluation conditions, 170°C or higher is considered preferable. 〇: 170°C or higher ×: Less than 170°C

[0113] <Granulation property> The granulation property was evaluated by dispersing the resin particles after the external addition treatment in water respectively and measuring the volume average particle diameter and particle size distribution with a Coulter counter "Multisizer III" (manufactured by Beckman Coulter). For the granulation property, it is preferable that the particle size distribution is 1.20 or less when the volume average particle diameter is 5.0 to 5.9 μm. ○: Particle size distribution is 1.20 or less ×: Particle size distribution is greater than 1.20

[0114] <Chargeability> 0.5 g of the resin particles after the external addition treatment and 10 g of a ferrite carrier (manufactured by Powdertech, F-150) were placed in a 50 ml glass bottle, which was conditioned at 23°C and a relative humidity of 50% for 8 hours or more, and then frictionally stirred at 90 rpm for 2 minutes with a turbler shaker mixer. 0.2 g of the mixed powder after stirring was loaded into a blow-off powder chargeability measuring device equipped with a 20 μm opening stainless steel wire mesh, and the chargeability of the remaining ferrite carrier was measured under the conditions of a blow pressure of 10 KPa and a suction pressure of 5 KPa, and the charge amount (μC / g) of the resin particles was calculated by a standard method. Note that for toner, the higher the negative charge amount, the better the charging characteristics. A blow-off chargeability measuring device [manufactured by Toshiba Chemical Corporation] was used for the measurement.

[0115] [Judgment criteria] ◎: Less than -20 〇: -20 or more and less than -15 ×: -15 or more

[0116] The resin particles of Examples 1 to 9 of the present invention exhibited excellent performance in terms of hot offset resistance, particle size distribution, and chargeability. On the other hand, the resin particles (D'-1) using the polyester resin (A'-1) with a number average molecular weight of less than 1000 had poor offset resistance. The resin particles (D'-2) using the polyester resin (A'-2) with a number average molecular weight exceeding 10,000 had poor granulation properties. The resin particles (D'-3) using the polyester resin (A'-3) not having the chemical structure portion represented by the above general formula (1) or (2) had poor chargeability.

Industrial Applicability

[0117] Since the polyester and resin particles of the present invention have good hot offset resistance, granulation properties, and chargeability, they are extremely useful as materials for toner for electrostatic charge image development used in electrophotography, electrostatic recording, electrostatic printing, etc.

Claims

1. A method for producing resin particles, comprising a step of bonding, in an aqueous medium, the chemical structural portion of general formula (1) or (2) of a polyester resin having a number average molecular weight of 1,000 to 10,000 and a chemical structural portion represented by the following general formula (1) and / or (2): 【Chemistry 1】 [In the general formulas (1) and (2), R １ represents a hydrogen atom or an alkyl group; R ２ each independently represents an alkylene group or an oxyalkylene group.

2. 2. The method for producing resin particles according to claim 1, wherein the metal compound is at least one selected from the group consisting of magnesium compounds, aluminum compounds, calcium compounds, titanium compounds, vanadium compounds, chromium compounds, manganese compounds, iron compounds, cobalt compounds, nickel compounds, copper compounds, zinc compounds and zirconium compounds.

3. The method for producing resin particles according to claim 1 or 2, wherein the polyester resin satisfies the relationship of the following mathematical formula (1): Number average molecular weight of polyester resin × number of moles (mol) of compound having a chemical structure represented by general formula (1) or (2) / weight (g) of all raw materials for polyester resin ≧ 0.5 (1)

4. The method for producing resin particles according to any one of claims 1 to 3, wherein a molar ratio [(S) / (T)] of the chemical structure portion (S) of the polyester resin represented by the general formula (1) and / or (2) to the metal compound (T) is 0.5 to 10.

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