JP3747930B2 - Method for producing toner particles - Google Patents

Description

  The present invention relates to a polyester polymerized toner, that is, a polyester-containing toner obtained by a wet polymerization method.

  At present, as a toner for electrophotography, a polyester toner obtained by a conventional so-called pulverization method and a polymer toner obtained by a wet method including a polymerization process are well known.

  Although the polyester toner obtained by the pulverization method has good heat-resistant storage properties, it is irregular, its particle size distribution is broad, fluidity is low, transferability is low, and fixing energy is high. was there. In particular, fixing is not suitable for oilless fixing because of low compatibility of wax and polyester resin.

  The polymerized toner generally contains a styrene-acrylic resin, and it is easy to form toner particles having a sharper particle size distribution than the toner particle size distribution by the pulverization method, and it is easy to encapsulate the wax. The fluidity can also be greatly improved. Also, since it is easy to obtain a spherical toner, transferability can be improved. Furthermore, the degree of freedom of Tg and melt viscosity of the binder resin is large, which is advantageous for oilless fixing. However, polymerized toners require a reduction in molecular weight and a decrease in Tg in order to aim at low-temperature fixing, resulting in deterioration of heat-resistant storage properties.

Accordingly, attention has been paid to polyester polymerized toner having both advantages. The polyester polymerized toner is a polyester-containing toner obtained by a wet polymerization method. The polyester polymerized toner cannot be obtained in the same manner as conventional polymerized toner because the raw material monomer of the polyester has water solubility. Therefore, toner particles are produced by dissolving or dispersing a prepolymer having an isocyanate group introduced into a polyester terminal with a diisocyanate compound in a solvent together with a pigment and wax, emulsifying it in an aqueous medium, performing interfacial polymerization, and removing the solvent. An interfacial polymerization method has been proposed (see, for example, Patent Documents 1 to 6).
JP 2002-351143 A Japanese Patent Laid-Open No. 11-149180 JP 2000-292981 A JP 2002-169336 JP JP 2002-287400 A JP 2002-351141 A

  During the interfacial polymerization, an amino group is generated by hydrolysis of the isocyanate group of the prepolymer at the interface between the oil droplet particles containing the isocyanate group-containing prepolymer and the aqueous medium, and the amino group reacts with the undecomposed isocyanate group. Thus, a urea bond is formed, and a hydroxyl group in the resin reacts with an isocyanate to form a urethane bond, and chain extension and / or crosslinking (high molecular weight) is performed.

  However, the urea bond and urethane bond formed in this way have a problem that moisture is easily adsorbed and the toner chargeability is highly dependent on the environment.

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a polyester polymer toner in which the toner charging property is less dependent on the environment and is not particularly affected by humidity.

  The present invention provides a method for producing a polyester polymerized toner in which no urethane bond or urea bond as described above is formed. The toner particles produced by the production method of the present invention are chain-extended by Diels-Alder reaction. Polyester having a crosslinked structure is formed as a binder resin, and a toner having a stable chargeability without being affected by humidity can be obtained.

The toner of the present invention is
(A) a step of forming a polyester prepolymer,
(B) Using the polyester prepolymer obtained in the step (A), a first reactive group-containing polyester prepolymer having a conjugated double bond capable of Diels-Alder reaction, and multiple bonds capable of Diels-Alder reaction Forming a second reactive group-containing polyester prepolymer having:
(C) An oily dispersion obtained by dissolving or dispersing a first reactive group-containing polyester prepolymer, a second reactive group-containing polyester prepolymer, and a desired toner additive in an organic solvent is dispersed in an aqueous medium. A step of preparing an oil-in-water (O / W) dispersion and forming a polyester binder resin that has undergone chain extension and crosslinking by Diels-Alder reaction,
(D) removing the organic solvent from the system to form resin particles, and drying the resin particles to obtain toner particles;
Can be produced by a process consisting of:

Hereafter, each process in the manufacturing method of the toner of this invention is demonstrated in detail.
Process (A)
First, the process for forming the polyester prepolymer will be described. The polyester prepolymer can be obtained by polycondensation of a polyol component and a polycarboxylic acid component.

  Among the polyol components, examples of the diol component include bis (4- (2-hydroxyethoxy) phenyl) hexafluoroisopropylidene, 4,4 ′-(3-hydroxypropyloxy) biphenyl, and bis (4- (2-hydroxy Bisphenol A alkylene oxide adducts such as ethoxy) phenyl) isopropylidene, bis (4- (3-hydroxypropyloxy) phenyl) isopropylidene, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3 -Propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol Polyethylene glycol, polytetramethylene glycol, bisphenol A, hydrogenated bisphenol A, and the like.

  Examples of the trivalent or higher polyol component include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol. 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, etc. And the above trivalent or higher valent hydroxy compounds and alkylene oxide adducts.

  Preferred polyol components are bis (4- (2-hydroxyethoxy) phenyl) hexafluoroisopropylidene, 4,4 ′-(3-hydroxypropyloxy) biphenyl, etc., in particular bis (4- (2-hydroxyethoxy) phenyl ) Hexafluoroisopropylidene, 4,4 ′-(3-hydroxypropyloxy) biphenyl.

  Examples of the dicarboxylic acid component among the polycarboxylic acid components include isophthalic acid, terephthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, cyclohexanedicarboxylic acid, succinic acid, adipic acid, Sebacic acid, azelaic acid, malonic acid, n-dodecenyl succinic acid, isododecenyl succinic acid, n-dodecyl succinic acid, isododecyl succinic acid, n-octenyl succinic acid, isooctenyl succinic acid, n-octyl succinic acid, isooctyl succinic acid Examples include acids, anhydrides of these acids, and lower alkyl esters.

  Examples of the trivalent or higher polycarboxylic acid component include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, 1,2,4 -Cyclohexanetricarboxylic acid, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, embol dimer acid, anhydrides of these acids, lower alkyl esters and the like.

  Preferred carboxylic acid components are isophthalic acid, terephthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, madipic acid and the like, particularly isophthalic acid and terephthalic acid.

  The polyester prepolymer can be obtained according to a conventional method. The degree of polymerization of the polyester prepolymer is not particularly limited as long as the molecular weight can be increased by the Diels-Alder reaction described later. However, since it is necessary to introduce a reactive group in a later step, the carboxyl group component is used in an excess equivalent to the hydroxy group component to produce a terminal carboxyl group polyester prepolymer, or the hydroxy group component is used from the carboxyl group component. An excess of equivalent weight is used to produce a terminal nidroxyl-based polyester prepolymer. In the former case, the excess degree is equivalent to 1 to 2 times, more preferably 1.05 to 1.5 times the equivalent of the hydroxy group component of the carboxyl group component. In the latter case, the excess degree is equivalent to 1-2 times the equivalent of the hydroxy group component, more preferably 1.05 to 1.5 times the equivalent of the carboxyl group component.

Process (B)
Using the polyester prepolymer obtained in the above step (A), a first reactive group-containing polyester prepolymer having a conjugated double bond capable of Diels-Alder reaction (hereinafter simply referred to as “first reactive group-containing”). Polyester prepolymer ”and a second reactive group-containing polyester prepolymer having multiple bonds capable of Diels-Alder reaction (hereinafter, simply referred to as“ second reactive group-containing polyester prepolymer ”) ).

First, the manufacturing method of the 1st reactive group containing polyester prepolymer is demonstrated.
When the first reactive group-containing polyester prepolymer is a terminal carboxyl group polyester prepolymer as the prepolymer obtained in step (A), for example, as shown in the following reaction formula 1, It is produced by deriving a terminal carboxyl group of a polyester prepolymer to an acid halide with thionyl chloride and reacting the acid halide with an alcohol compound having a conjugated double bond capable of Diels-Alder reaction (for example, furfuryl alcohol). obtain.

  When a polyester prepolymer having a terminal hydroxyl group is used as the prepolymer, for example, as shown in the following reaction formula 2, the prepolymer is reacted with an acid halide having a conjugated double bond capable of Diels-Alder reaction. (For example, the following reaction formula 2).

Specific examples of the first reactive group-containing polyester prepolymer include compounds having the following structural formula.

  The second reactive group-containing polyester prepolymer, for example, as shown in the following reaction formula 3, when a polyester prepolymer having a terminal hydroxyl group is used as the prepolymer obtained in the step (A), the polyester It can be produced by reacting a prepolymer with an acid chloride having multiple bonds capable of Diels-Alder reaction, such as acrylic acid chloride.

  When using a polyester prepolymer having a terminal carboxyl group as the prepolymer obtained in the step (A), as shown in the following reaction formula 4, the terminal carboxyl group of the polyester prepolymer is first converted to an acid halide with thionyl chloride. It can be prepared by reacting and reacting the acid halide with an alcohol compound having multiple bonds capable of Diels-Alder reaction, such as 2-hydroxyethyl acrylate. The induction to the acid halide is the same as described in Reaction Scheme 1.

Specific examples of the second reactive group-containing polyester prepolymer include compounds having the following structural formula.

  A group having a conjugated double bond capable of Diels-Alder reaction and a group having multiple bonds capable of Diels-Alder reaction may be contained in the same polyester prepolymer (hereinafter referred to as “third reactive group-containing polyester prepolymer”). Such a polyester prepolymer can be synthesized by the following reaction formulas 5 and 6. In this case, the contents described in the reaction formulas 1 to 4 may be referred to.

  Specific examples of the third reactive group-containing polyester prepolymer include compounds having the following structural formula.

Process (C)
In step (C), the first reactive group-containing polyester prepolymer obtained in step (B), the second reactive group-containing polyester prepolymer, and the desired toner additive are dissolved or dispersed in an organic solvent. The oily dispersion is dispersed in an aqueous medium to prepare an oil-in-water (O / W type) dispersion, and a Diels-Alder reaction is performed.

  The first reactive group-containing polyester prepolymer and the second reactive group-containing polyester prepolymer have an equivalent amount of a conjugated double bond group capable of Diels-Alder reaction and a multiple bond group capable of Diels-Alder reaction. Mix in such an amount. When the first and second reactive group-containing polyester prepolymers are derived from a polyester prepolymer produced under the same production conditions such as pressure, temperature, and polymerization time, they may be mixed at the same weight. .

  As the organic solvent used in the oil-soluble dispersion, a solvent in which the first and second reactive group-containing prepolymers are dissolved and insoluble in water, hardly soluble or slightly soluble is used. The boiling point is usually 60 to 150 ° C, preferably 70 to 120 ° C. Specific examples of the organic solvent include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, and acetic acid. Methyl, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone and the like can be used alone or in combination of two or more. In particular, ethyl acetate having good solubility and volatilization removal property is preferable. The organic solvent is usually used in an amount of 50 to 900 parts by weight with respect to 100 parts by weight of the total amount of the first and second reactive group-containing prepolymers.

  Examples of the toner additive added to the oil dispersion include a colorant, a charge control agent, a release agent, and a polymer compound, a plasticizer, and an antioxidant as necessary.

  Various conventionally known pigments can be used as the colorant that can be contained in the oil dispersion. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), CI pigment yellow 74, cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow , Polyazo Yellow, Oil Yellow, Hansa Yellow (GR, A, RN, R), Pigment Yellow L, Benzidine Yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake , Quinoline yellow lake, anthrazan yellow BGL, isoindolinone yellow, bengara, red lead, lead vermilion, CI pigment red 122, cadmium red, cadmium mercurial red, antimony vermilion, permanent red 4R, para red, phise red, para Lortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carnmin BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Tolujing Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oil Red, Quinacridone Red, Pi Lazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indance Ren blue (RS, BC), indigo, ultramarine, bitumen, CI pigment blue 15: 3, anthraquinone blue, fast violet B, methyl violet lake, cobalt purple, manganese purple, dioxane violet, anthraquinone violet, chrome green, zinc green, Chrome oxide, pyridian, emerald green, pigment green B, naphthol green B, green gold, acid Lean lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, ritbon and mixtures thereof can be used. As the colorant, masterbatch colorant particles dispersed in a separate solvent may be used. The colorant is usually used so that the content in the toner is 1 to 15% by weight, preferably 1 to 10% by weight, based on the whole toner.

  Various conventionally known release agents can be used as the release agent that can be contained in the oil dispersion. As such, for example, polyolefin wax such as polyethylene wax and polypropylene wax, paraffin wax, long chain hydrocarbon wax such as sazol wax, dialkyl ketone wax such as distearyl ketone, carnauba wax, Montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18-octadecanediol distearate, tristearyl trimellitic acid, distearyl Examples thereof include ester waxes such as maleate, and amide waxes such as ethylenediamine dibehenyl amide and trimellitic acid tristearyl amide. The melting point of the wax is usually 40 to 160 ° C, preferably 50 to 120 ° C, more preferably 60 to 90 ° C. A wax having a melting point of less than 40 ° C. has an adverse effect on heat-resistant storage stability, and a wax having a melting point of more than 160 ° C. is liable to cause cold offset at the time of fixing at a low temperature and is not suitable for low-temperature fixability. The content of the wax in the toner is preferably 5 to 30% by weight.

  Various known charge control agents can be used in the oil dispersion. Examples include nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified quaternary ammonium salts). ), Alkylamide, simple substance or compound of phosphorus, simple substance or compound of tungsten, fluorine-based activator, metal salt of salicylic acid, metal salt of salicylic acid derivative, and the like. Specifically, Nitronine dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, phenolic condensate E-89 (above, Orient Chemical Industries), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, Hodogaya Chemical Co., Ltd.), quaternary ammonium Copy charge PSY VP2038 of salt, copy blue PR of triphenylmethane derivative, copy charge NEG VP2036 of quaternary ammonium salt, copy charge NX VP434 (above, manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit Co., Ltd.), copper phthalocyanine, perylene, quinacridone, azo pigments, and other polymer compounds having functional groups such as sulfonic acid groups, carboxyl groups, and quaternary ammonium salts Etc. The. The amount of charge control agent used is determined primarily by the type of binder resin in the toner, the presence or absence of additives used as necessary, and the toner production method including the dispersion method, and is uniquely limited. Although not intended, the amount is preferably such that the content in the toner is 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight with respect to 100 parts by weight of the binder resin.

  The plasticizer that can be contained in the oil dispersion is used to adjust the thermal properties and the elastic modulus of the toner. Examples thereof include phthalates [dibutyl phthalate, dioctyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, etc.], aliphatic dibasic acid esters [di-2-ethylhexyl adipate, sebacic acid-2- Ethylhexyl etc.], trimellitic ester [trimellitic acid tri-2-ethylhexyl, trimellitic acid trioctyl etc.], phosphoric acid ester [triethyl phosphate, tri-2-ethylhexyl phosphate, tricresyl phosphate etc.], fatty acid ester [olein Acid butyl etc.] and a mixture of two or more thereof. The plasticizer is used in an amount of about 0.1 to 5% by weight with respect to the oil-soluble component.

  Polyester may be used as the polymer compound added to the oil dispersion if necessary. As such a polyester, for example, a polyester composed of a polyol component and a polycarboxylic acid component as described in the description of the step (A) can be used. The degree of polymerization of the polyester is not particularly limited. The amount of such polyester used is not particularly limited as long as the object of the present invention is achieved, and usually 10 to 60 parts by weight with respect to 100 parts by weight of the total amount of the first and second reactive group-containing prepolymers. Is preferred. Such a polymer compound is used to adjust the thermal properties and elastic modulus of the toner. In addition to polyester, polystyrene, polymethylmethyl methacrylate, polyvinyl alcohol (PVA), polyethylene, polypropylene, and styrene-butyl acrylate are used. Copolymers, vinyl polymer such as styrene-butyl acrylate-methacrylic acid copolymer, ethylene-styrene copolymer, polyamide of 6-nylon, 6,6-nylon, (isophthalic acid, oxalic acid, cyclohexanediamine), etc. Polyamides of (m-xylylene diisocyanate, 1,6-hexanediol), polyurethanes of (m-xylylene diisocyanate, isophorone diisocyanate, 1,6-hexanediol, bisphenol A) Polyurea such as urethane, polyurea of (m-xylylene diisocyanate, 2,5-hexanediamine), polyurea of (isophorone diisocyanate, 1,4-cyclohexanediamine, 2,5-hexanediamine), (pyromellitic dianhydride) Products, 2,5-hexanediamine, 1,4-cyclohexanediamine) polyamic acid or polyimide, (tricarboxylcyclobutanesuccinic dianhydride, diaminodiphenyl ether) polyamic acid or polyimide such as polyamic acid or polyimide, polyethylene glycol, Polytetramethylene ether, polyether such as polyphenylene ether, polysulfone such as polyphenylsulfone and polyethylenesulfone, polyphenylsulfide, polyethylenesulfur Polysulfides, such as de or copolymers of these polymers, (polyester chromatography amides, polyurethanes chromatography urea, polyester over urethane, polyether chromatography urethanes, polyesters chromatography ether over urethane, and the like), or the like can be used.

  Antioxidants added to the oil dispersion as necessary include the above-mentioned plasticizers and 2,6-di-tert-butyl-p-cresol, n-octadecyl-3- (3,5-di-tert-butyl). Hindered phenol compounds such as -4-hydroxyphenyl) propionate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1- [2- [3- (3,5-di-t -Butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-t-butyl-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, etc. Hindered amine compounds, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazol Benzotriazoles such as equal can be used, the oil-soluble component, 0.01 to 30 wt%, and preferably about 0.05 to 10 wt%.

  The solvent used in the aqueous medium may be water alone, or a solvent miscible with water may be used in combination. Examples of the miscible solvent include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methylcellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.) and the like.

  In the aqueous medium, in order to stabilize the organic solvent dispersion containing the prepolymer, an emulsifier, a dispersant, inorganic fine particles, or organic fine particles may coexist. A catalyst such as an acid or a base may be added to promote the Diels Alder reaction of the prepolymer.

  As inorganic fine particles that are optionally added to the aqueous medium, various conventionally known inorganic compounds that are insoluble or hardly soluble in water are used. Examples of such materials include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite.

  As the organic fine particles to be optionally present in the aqueous medium, various conventionally known polymer fine particles which are insoluble or hardly soluble in water are used. Examples of such materials include fine particles of hydrophobic polymers such as hydrocarbon resins, fluorine-containing resins, and silicone resins.

  The particle size of the inorganic or organic fine particles is usually smaller than the particle size of the toner, and from the viewpoint of particle size uniformity, the value of the particle size ratio [volume average particle size of fine particles] / [volume average particle size of toner] Is preferably in the range of 0.001 to 0.3. If the particle size ratio is larger than 0.3, fine particles are not efficiently adsorbed on the surface of the toner, so that the particle size distribution of the obtained toner tends to be wide. The volume average particle diameter of the inorganic or organic fine particles can be appropriately adjusted within the above range of the particle diameter ratio so as to be a particle diameter suitable for obtaining a toner having a desired particle diameter. For example, when it is desired to obtain a toner having a volume average particle diameter of 5 μm, it is preferably 0.0025 to 1.5 μm, particularly preferably in the range of 0.005 to 1.0 μm, and preferably when a toner of 10 μm is obtained. Is 0.005 to 3 μm, particularly preferably 0.05 to 2 μm. Further, when such inorganic or organic fine particles are added, it is used in an amount of 0.1 to 3% by weight, preferably about 0.1 to 1% by weight, based on the toner weight.

  As the emulsifier or dispersant, conventionally known surfactants, hydrophilic polymers that serve as protective colloids, and the like can be used.

  Examples of the surfactant include an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant. The surfactant may be a combination of two or more surfactants.

  Examples of the anionic surfactant include carboxylic acid or a salt thereof, sulfate ester salt, salt of carboxymethylated product, sulfonate salt and phosphate ester salt.

Examples of carboxylic acids or salts thereof include saturated or unsaturated fatty acids having 8 to 22 carbon atoms or salts thereof. Specifically, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and behenic acid. , Oleic acid, linoleic acid, ricinoleic acid and a mixture of higher fatty acids obtained by saponifying coconut oil, palm kernel oil, rice bran oil, beef tallow and the like. Examples of the salt include salts of sodium, potassium, ammonium, alkanolamine and the like.

  Examples of sulfate salts include higher alcohol sulfate esters (sulfate esters of aliphatic alcohols having 8 to 18 carbon atoms) and higher alkyl ether sulfate esters salts (1 to 10 moles of ethylene oxide of aliphatic alcohols having 8 to 18 carbon atoms). Sulfates of adducts), sulfated oils (natural unsaturated oils or unsaturated waxes that have been neutralized by sulfation), sulfated fatty acid esters (sulfurized lower alcohol esters of unsaturated fatty acids) And sulphated olefins (sulphated and neutralized olefins having 12 to 18 carbon atoms). Examples of the salt include sodium salt, potassium salt, ammonium salt, and alkanolamine salt. Specific examples of higher alcohol sulfates include octyl alcohol sulfate, decyl alcohol sulfate, lauryl alcohol sulfate, stearyl alcohol sulfate, alcohols synthesized using Ziegler catalysts (for example, ALFOL 1214: CONDEA's sulfate ester salt, alcohols synthesized by the oxo method (for example, Dovanol 23, 25, 45: Mitsubishi Yuka, Tridecanol: Kyowa Hakko, Oxocol 1213, 1215, 1415: Nissan Chemical, Diadol 115 -L, 115H, 135: manufactured by Mitsubishi Chemical); specific examples of higher alkyl ether sulfates include lauryl alcohol ethylene oxide 2-mole adduct sulfate, octyl alcohol ethyl Oxide 3-mole adduct sulfate ester; Specific examples of sulfated oils include sodium, potassium, ammonium, alkanolamine salts sulfated fatty acids of castor oil, peanut oil, olive oil, rapeseed oil, beef tallow, sheep fat, etc. Specific examples of the ester include sodium, potassium, ammonium, and alkanolamine salts of sulfates such as butyl oleate and butyl ricinoleate; specific examples of the sulfated olefin include Typol (manufactured by Shell).

Examples of the carboxymethylated salt include a carboxymethylated salt of an aliphatic alcohol having 8 to 16 carbon atoms and a carboxymethylated salt of an ethylene oxide 1 to 10 mol adduct of an aliphatic alcohol having 8 to 16 carbon atoms. It is done. Specific examples of carboxymethylated salts of aliphatic alcohols include octyl alcohol carboxymethylated sodium salt, decyl alcohol carboxymethylated sodium salt, lauryl alcohol carboxymethylated sodium salt, dovanol 23 carboxymethylated sodium salt, tridecanol Specific examples of salts of carboxymethylated sodium salt of carboxymethylated product of aliphatic alcohol ethylene oxide 1-10 mol adduct include octyl alcohol ethylene oxide 3 mol adduct carboxymethylated sodium salt, lauryl alcohol ethylene oxide 4 Mole adduct carboxymethylated sodium salt, dovanol 23 ethylene oxide 3 mol adduct carboxymethylated sodium salt, tridecanol ethylene oxide Such as 5 mole adduct carboxymethylated sodium salt.

  Examples of the sulfonate include alkylbenzene sulfonate, alkyl naphthalene sulfonate, sulfosuccinic acid diester type, α-olefin sulfonate, Igepon T type, and sulfonates of other aromatic ring-containing compounds. Specific examples of alkylbenzene sulfonate include sodium dodecylbenzene sulfonate; specific examples of alkyl naphthalene sulfonate; sodium dodecyl naphthalene sulfonate; specific examples of sulfosuccinic acid diester type include di-2 sulfosuccinic acid di-2 -Ethylhexyl ester sodium salt and the like. Examples of the sulfonate of the aromatic ring-containing compound include mono- or disulfonate of alkylated diphenyl ether, styrenated phenol sulfonate, and the like.

  Examples of phosphoric acid ester salts include higher alcohol phosphoric acid ester salts and higher alcohol ethylene oxide adduct phosphoric acid ester salts.

  Specific examples of higher alcohol phosphoric acid ester salts include lauryl alcohol phosphoric acid monoester disodium salt, lauryl alcohol phosphoric acid diester sodium salt; specific examples of higher alcohol ethylene oxide adduct phosphoric acid ester salts include oleyl alcohol ethylene oxide 5 mol adduct phosphate monoester disodium salt.

Examples of the cationic surfactant include a quaternary ammonium salt type and an amine salt type.

  The quaternary ammonium salt type is obtained by a reaction between a tertiary amine and a quaternizing agent (an alkylating agent such as methyl chloride, methyl bromide, ethyl chloride, benzyl chloride, dimethyl sulfate; ethylene oxide, etc.) For example, lauryl trimethyl ammonium chloride, didecyl dimethyl ammonium chloride, dioctyl dimethyl ammonium bromide, stearyl trimethyl ammonium bromide, lauryl dimethyl benzyl ammonium chloride (benzalkonium chloride), cetyl pyridinium chloride, polyoxyethylene trimethyl ammonium chloride, stearamide ethyl diethyl Examples include methylammonium methosulfate.

  As amine salt type, primary to tertiary amines are inorganic acids (hydrochloric acid, nitric acid, sulfuric acid, hydroiodic acid, etc.) or organic acids (acetic acid, formic acid, oxalic acid, lactic acid, gluconic acid, adipic acid, alkylphosphoric acid, etc.) It is obtained by neutralizing with For example, the primary amine salt type includes inorganic or organic acid salts of higher aliphatic amines (higher amines such as laurylamine, stearylamine, cetylamine, hardened tallow amine, and rosinamine); Examples include fatty acid (stearic acid, oleic acid, etc.) salts and the like. Examples of the secondary amine salt type include inorganic acid salts or organic acid salts such as ethylene oxide adducts of aliphatic amines. Examples of the tertiary amine salt type include aliphatic amines (triethylamine, ethyldimethylamine, N, N, N ′, N′-tetramethylethylenediamine, etc.), ethylene oxides of aliphatic amines (2 moles). Above) Adducts, alicyclic amines (N-methylpyrrolidine, N-methylpiperidine, N-methylhexamethyleneimine, N-methylmorpholine, 1,8-diazabicyclo (5,4,0) -7-undecene, etc.) , Inorganic acid salts or organic acid salts of nitrogen-containing heterocyclic aromatic amines (4-dimethylaminopyridine, N-methylimidazole, 4,4′-dipyridyl, etc.); triethanolamine monostearate, stearamide ethyl diethyl methyl ethanol Examples include inorganic acid salts or organic acid salts of tertiary amines such as amines.

  Examples of amphoteric surfactants used in the present invention include carboxylate-type amphoteric surfactants, sulfate ester-type amphoteric surfactants, sulfonate-type amphoteric surfactants, and phosphate ester-type amphoteric surfactants. It is done.

Examples of the carboxylate-type amphoteric surfactants include amino acid-type amphoteric surfactants, betaine-type amphoteric surfactants, and imidazoline-type amphoteric surfactants. Examples of amphoteric surfactants having an amino group and a carboxyl group include compounds represented by the following general formula.
[R ₄ —NH— (CH ₂ ) _p —COO] _q M
[Wherein R ₄ is a monovalent hydrocarbon group; p is usually 1 or 2; q is 1 or 2; M is a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium cation, an amine cation, an alkanolamine. Such as cations. ].

Specifically, for example, an alkylaminopropionic acid type amphoteric surfactant (sodium stearylaminopropionate, sodium laurylaminopropionate, etc.); an alkylaminoacetic acid type amphoteric surfactant (such as sodium laurylaminoacetate), etc. .
Betaine-type amphoteric surfactants are amphoteric surfactants having a quaternary ammonium salt-type cation moiety and a carboxylic acid-type anion moiety in the molecule. For example, alkyldimethylbetaine (stearyl) represented by the following general formula: Dimethylaminoacetic acid betaine, lauryl dimethylaminoacetic acid betaine, etc.), amide betaine (coconut oil fatty acid amide propyl betaine etc.), alkyl dihydroxyalkyl betaine (lauryl dihydroxyethyl betaine etc.) etc. are mentioned.

  Furthermore, examples of the imidazoline type amphoteric surfactant include 2-undecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine.

  Examples of other amphoteric surfactants include glycine-type amphoteric surfactants such as sodium lauroyl glycine, sodium lauryl diaminoethyl glycine, lauryl diaminoethyl glycine hydrochloride, dioctyl diaminoethyl glycine hydrochloride; pentadecylsulfotaurine and the like Examples include sulfobetaine-type amphoteric surfactants.

  Nonionic surfactants include alkylene oxide addition type nonionic surfactants and polyhydric alcohol type nonionic surfactants.

Alkylene oxide addition type nonionic surfactants include polyalkylene glycols obtained by adding alkylene oxide directly to higher alcohols, higher fatty acids or alkylamines, or by adding alkylene oxides to glycols. It is obtained by reacting a higher fatty acid with a higher fatty acid, adding an alkylene oxide to an esterified product obtained by reacting a higher fatty acid with a polyhydric alcohol, or adding an alkylene oxide to a higher fatty acid amide. Examples of the alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide. Of these, preferred are ethylene oxide and random or block adducts of ethylene oxide and propylene oxide. The number of moles of alkylene oxide added is preferably 10 to 50 moles, and 50 to 100% by weight of the alkylene oxide is preferably ethylene oxide.

  Specific examples of the alkylene oxide addition type nonionic surfactant include oxyalkylene alkyl ethers (for example, octyl alcohol ethylene oxide addition product, lauryl alcohol ethylene oxide addition product, stearyl alcohol ethylene oxide addition product, oleyl alcohol ethylene oxide addition product). , Lauryl alcohol ethylene oxide propylene oxide block adduct, etc.); polyoxyalkylene higher fatty acid ester (eg, stearyl acid ethylene oxide adduct, lauric acid ethylene oxide adduct, etc.); polyoxyalkylene polyhydric alcohol higher fatty acid ester (For example, polyethylene glycol lauric acid diester, polyethylene glycol oleic acid diester, polyethylene glycol Polyoxyalkylene alkylphenyl ether (eg, nonylphenol ethylene oxide adduct, nonylphenol ethylene oxide propylene oxide block adduct, octylphenol ethylene oxide adduct, bisphenol A ethylene oxide adduct, dinonylphenol ethylene oxide addition) Polyoxyalkylene alkylamino ether and (for example, laurylamine ethylene oxide adduct, stearylamine ethylene oxide adduct, etc.); polyoxyalkylene alkyl alkanolamide (for example, Hydroxyethyl lauric acid amide ethylene oxide adduct, hydroxypropyl oleic acid Ethylene oxide adducts of bromide, ethylene oxide adducts of dihydroxy ethyl lauric acid amide, etc.) and the like.

  Examples of the polyhydric alcohol type nonionic surfactant include polyhydric alcohol fatty acid esters, polyhydric alcohol fatty acid ester alkylene oxide adducts, polyhydric alcohol alkyl ethers, and polyhydric alcohol alkyl ether alkylene oxide adducts.

  Specific examples of polyhydric alcohol fatty acid esters include pentaerythritol monolaurate, pentaerythritol monooleate, sorbitan monolaurate, sorbitan monostearate, sorbitan monolaurate, sorbitan dilaurate, sorbitan dioleate, sucrose monostearate, etc. Is mentioned. Specific examples of the polyhydric alcohol fatty acid ester alkylene oxide adduct include ethylene glycol monooleate ethylene oxide adduct, ethylene glycol monostearate ethylene oxide adduct, trimethylolpropane monostearate ethylene oxide propylene oxide random adduct, sorbitan mono Examples include laurate ethylene oxide adduct, sorbitan monostearate ethylene oxide adduct, sorbitan distearate ethylene oxide adduct, sorbitan dilaurate ethylene oxide propylene oxide random adduct, and the like. Specific examples of the polyhydric alcohol alkyl ether include pentaerythritol monobutyl ether, pentaerythritol monolauryl ether, sorbitan monomethyl ether, sorbitan monostearyl ether, methyl glycoside, lauryl glycoside and the like. Specific examples of polyhydric alcohol alkyl ether alkylene oxide adducts include sorbitan monostearyl ether ethylene oxide adduct, methylglycoside ethylene oxide propylene oxide random adduct, lauryl glycoside ethylene oxide adduct, stearyl glycoside ethylene oxide propylene oxide random adduct Etc.

  Preferable emulsifiers or dispersants that do not decompose even at a temperature of about 200 ° C., such as sodium dodecylbenzene sulfate and sodium dodecyldiphenyl ether disulfonate.

  The emulsifier or dispersant is 0.1 to 5% by weight, preferably 0.2 to 2% by weight, based on the toner composition.

  By using a part of the hydrophilic polymer, a high-molecular protective colloid can be formed, and the amount of the emulsifier to be used can be reduced.

  Hydrophilic polymers include acids such as acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride, or hydroxyl groups (meta ) Acrylic monomers such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate , 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate Luric acid esters, N-methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, etc., or compounds containing vinyl alcohol and a carboxyl group Esters such as vinyl acetate, vinyl propionate, vinyl butyrate, acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, pinyl pyridine, vinyl pyrrolidone, vinyl imidazole , Homopolymers or copolymers such as those having a nitrogen atom such as ethyleneimine or a heterocyclic ring thereof, polyoxyethylene, polyoxypropylene , Polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxy Examples include polyoxyethylenes such as ethylene nonylphenyl ester, celluloses such as methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and gelatins such as phthalated gelatin. do it.

Acids and bases as catalysts that are optionally added to promote the Diels Alder reaction of the prepolymer include concentrated HCl, dry HCl, PPA (polyphosphoric acid), Lewis acids such as boroboric acid, ZnCl ₂ , AlCl ₃ , Metal halides such as Cu ₂ Cl ₃ and CsF can be preferably used.

  The amount of the aqueous medium used is usually 50 to 2000 parts by weight, preferably 100 to 1000 parts by weight, based on 100 parts by weight of a solid such as a prepolymer, a colorant, and a release agent contained in the oil dispersion. If the amount is less than 50 parts by weight, the toner solids are not well dispersed, and toner particles having a predetermined particle diameter cannot be obtained. If it exceeds 2000 parts by weight, it cannot be produced efficiently.

  The dispersion apparatus for dispersing the oil dispersion in the aqueous medium is not particularly limited, but is not particularly limited as long as it is generally commercially available as an emulsifier or a disperser. For example, a homogenizer (IKA) ), Polytron (manufactured by Kinematica), TK auto homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), etc., Ebara milder (manufactured by Aihara Seisakusho), TK fill mix, TK pipeline homomixer ( Special Kika Kogyo Co., Ltd.), colloid mill (Shinko Pantech Co., Ltd.), thrasher, trigonal wet milling machine (Mitsui Miike Kako Co., Ltd.), Captron (Eurotech Co., Ltd.), Fine Flow Mill (Pacific Kiko Co., Ltd.) ) And other continuous emulsifiers, microfluidizer (manufactured by Mizuho Kogyo Co., Ltd.), nanomizer (manufactured by Nanomizer), APV Gaurin ( High pressure emulsifiers such as Urine), membrane emulsifiers such as membrane emulsifiers (made by Chilling Industries), vibratory emulsifiers such as Vibro mixers (made by Chilling Industries), ultrasonic homogenizers (made by Branson) And an ultrasonic emulsifier. Among these, APV Gaurin, homogenizer, TK auto homomixer, Ebara milder, TK fill mix, and TK pipeline homomixer are preferable from the viewpoint of uniform particle size.

  The Diels-Alder reaction may be carried out by continuously dispersing and stirring the system temperature under normal pressure at −100 to 300 ° C., preferably 100 to 250 ° C. for 1 to 1800 minutes, preferably 120 to 600 minutes. . By heating, the viscosity of the dispersion can be lowered, and uniform dispersion becomes possible.

In the Diels-Alder reaction, the first polyester prepolymer having a conjugated double bond capable of Diels-Alder reaction and the second polyester prepolymer having multiple bonds capable of Diels-Alder reaction are reacted in oil droplets to cause chain extension. Crosslinking (high molecular weight) is achieved .

  The polyester binder resin finally obtained is subjected to Diels-Alder reaction so that the glass transition point (Tg) is 50 ° C. or higher and the softening point (Tm) is 90 to 110 ° C. However, Tg means a value measured by DSC method (second run shoulder value), and Tm means a flow tester method.

Process (D)
After the Diels-Alder reaction, the organic solvent is removed from the system to form resin particles, and the resin particles are dried to obtain toner particles.

  The method for removing the organic solvent from the system is not particularly limited. For example, a method of gradually raising the temperature of the entire system and evaporating and removing the organic solvent under reduced pressure can be employed. At this time, the degree of toner circularity can be controlled by the strength and time of stirring during the temperature rise. By slowly removing the solvent, the shape becomes more spherical, and the average circularity is 0.980 or more. When the solvent is removed with strong stirring in a short time, the shape becomes irregular or irregular, and becomes 0.900 to 0.950 in terms of average circularity. By emulsifying and dispersing in an aqueous medium and further reacting the system (emulsified liquid) in the liquid removal medium while stirring with a stirring tank at a temperature of 30 to 50 ° C. and a strong stirring force, Shape control in the range of 0.850 to 0.990 is possible. This is thought to be due to volumetric shrinkage caused by abrupt removal of an organic solvent such as ethyl acetate contained in the granulation.

本明細書中、平均円形度はFIPA-2000（Sysmex社製）によって測定された値を用いている。しかし、上記装置によって測定されなければならないというわけではなく、上記式に基づく円形度を測定可能な装置であればいかなる装置によって測定されてもよい。 The average circularity is an average value of circularity expressed by the following formula.

In this specification, the average circularity is a value measured by FIPA-2000 (manufactured by Sysmex). However, it does not have to be measured by the above device, and any device that can measure the circularity based on the above formula may be used.

  The organic solvent can be removed by spraying the emulsified dispersion as a system in a dry atmosphere to completely remove the organic solvent and drying to form toner particles.

  Further, after the organic solvent is removed by evaporation, the reslurry washing in which the obtained resin particles are filtered and redispersed in pure water may be repeated. It is also possible to remove the dispersant, dispersion stabilizer, etc. adhering to the toner particle surface. In particular, when an inorganic fine particle as a dispersion stabilizer is used that is soluble in acid or alkali such as calcium phosphate salt, the inorganic fine particle such as calcium phosphate salt is dissolved with an acid such as hydrochloric acid, and then reslurry washing is performed. Good.

  Further, the dispersion immediately after the removal of the organic solvent or immediately after the reslurry washing can be subjected to a classification operation to adjust the particle size distribution of the obtained toner particles. In the classification operation in this case, the fine particle portion can be removed in the liquid by a cyclone, a decanter, centrifugation, or the like. Of course, the classification operation may be performed after obtaining the powder as a powder after drying. The dispersing agent and dispersion stabilizer on the toner particle surface can also be removed by classification operation.

In general, inorganic particles are preferably externally added as external additives to the toner particles after drying in order to assist fluidity, developability and chargeability. The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, and particularly preferably 5 nm to 500 nm. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g. The use ratio of the inorganic fine particles is preferably 0.01 to 5% by weight, more preferably 0.01 to 2.0% by weight, based on the toner particles. Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, diatomaceous earth. Examples include soil, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.

  Polymeric fine particles can also be used as an external additive. Examples of such materials include polystyrene obtained by soap-free emulsion polymerization, suspension polymerization, and dispersion polymerization, methacrylic acid ester and acrylic acid ester copolymers, polycondensation systems such as silicone, benzoguanamine, and nylon, and thermosetting resins. Examples include polymer particles.

  Such an external additive can be surface-treated to increase hydrophobicity and prevent deterioration of its flow characteristics and charging characteristics even under high humidity. Preferred examples of the surface treatment agent include silane coupling agents, silylating agents, silane coupling agents having a fluorinated alkyl group, organic titanate coupling agents, aluminum coupling agents, silicone oils, and modified silicone oils. Can be mentioned.

  Further, the toner particles may be externally added with a cleaning property improving agent for removing the developer after transfer remaining on the photoreceptor or the primary transfer medium. Examples of the cleaning property improver include polymer fine particles produced by soap-free emulsion polymerization such as fatty acid metal salts such as zinc stearate, calcium stearate and stearic acid, for example, polymethyl methacrylate fine particles and polystyrene fine particles. it can. The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm.

  The toner particles may be externally added with fine particles such as a release agent and a charge control agent.

  When the toner particles after drying are mixed with different kinds of particles such as external additives as described above, the different kinds of particles are fixed on the surface of the toner particles by applying a mechanical impact force to the mixed powder. , And detachment of foreign particles from the surface of the resulting composite particles can be prevented. Specific means include a method of applying an impact force to the mixture by blades rotating at high speed, a method of injecting and accelerating the mixture into a high-speed air stream, and causing particles or composite particles to collide with an appropriate collision plate, etc. is there. As equipment, Ong mill (manufactured by Hosokawa Micron Co., Ltd.), I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) has been modified to reduce the pulverization air pressure, hybridization system (manufactured by Nara Machinery Co., Ltd.), kryptron System (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar, etc.

  The toner of the present invention can be used as a two-component developer or a one-component developer that does not use a carrier.

  When the toner of the present invention is used for a two-component developer, it may be used by mixing with a magnetic carrier. The carrier to toner content ratio in the developer is preferably 1 to 10 parts by weight of toner with respect to 100 parts by weight of carrier. As the magnetic carrier, conventionally known ones such as iron powder, ferrite powder, magnetite powder, magnetic resin carrier having a particle diameter of about 20 to 200 μm can be used. Examples of the coating material include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Polyvinyl and polyvinylidene resins such as acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins and styrene acrylic copolymer resins, Halogenated olefin resins such as vinyl, polyester resins such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resins, polyethylene resins, polyvinyl fluoride resins, polyvinylidene fluoride resins, polytrifluoroethylene resins, polyhexafluoro Propylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinylidene fluoride And fluoro such as terpolymers of non-fluoride monomers including, and silicone resins. Moreover, you may make conductive powder etc. contain in coating resin as needed. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide or the like can be used. These conductive powders preferably have an average particle diameter of 1 μm or less. When the average particle diameter is larger than 1 μm, it becomes difficult to control electric resistance.

  Further, when the toner of the present invention is used as a one-component developer, it can be used as a magnetic toner or a non-magnetic toner.

  According to the present invention, it is possible to produce a polyester polymerized toner that is less dependent on the environment of toner chargeability and that is not particularly affected by humidity.

  The invention is further illustrated by the following examples, which are not intended to be disclosed with the intention of limiting the invention to the examples described. Hereinafter, “part” means “part by weight” unless otherwise specified.

Example 1
(Example of polyester production)
In a reaction vessel equipped with a condenser, stirrer and nitrogen inlet tube, 424 parts of bis (4- (2-hydroxyethoxy) phenyl) hexafluoroisopropylidene, 66.4 parts of terephthalic acid, 92.96 parts of isophthalic acid and C 10.56 parts of ₄ F ₉ C ₂ H ₄ OH was added and polycondensed at 200 ° C. for 10 hours under normal pressure. Next, the mixture was reacted for 5 hours while dehydrating at a reduced pressure of 10 to 15 mmHg to obtain polyester (a).

(Prepolymer Production Example-1)
424 parts of bis (4- (2-hydroxyethoxy) phenyl) hexafluoroisopropylidene and 232.4 parts of terephthalic acid are placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and at 200 ° C. under normal pressure. The polycondensation was performed for 10 hours. Next, the reaction was carried out for 5 hours while dehydrating at a reduced pressure of 10 to 15 mmHg to obtain a polyester prepolymer (b1) having a terminal carboxyl group.

  120 parts of thionyl chloride was added to a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction tube, and 20 parts of dimethylacetamide (DMAc) was slowly added under ice cooling. Next, 164 parts of the above polyester (b1) powder was rubbed at room temperature and heated and refluxed at normal pressure for 8 hours for chlorination reaction. Excess thionyl chloride and DMAc were removed under reduced pressure to obtain a terminal acid chloride polyester prepolymer (1-1).

  Further, 300 parts of ethyl acetate was added thereto, and while stirring at room temperature, a solution of 100 parts of DMAc in which 86.5 parts of furfuryl alcohol was dissolved was gradually added and reacted at room temperature for 4 hours. After the reaction, ethyl acetate, DMAc and excess furfuryl alcohol were removed under reduced pressure to obtain polyester (C-1) having a furan group at the terminal.

(Prepolymer Production Example-2)
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 339.2 parts of bis (4- (2-hydroxyethoxy) phenyl) hexafluoroisopropylidene, 4,4 ′-(3-hydroxypropyloxy) biphenyl 138 parts and 166 parts of terephthalic acid were polycondensed at 200 ° C. for 10 hours under normal pressure. Next, the reaction product was reacted for 5 hours while dehydrating at a reduced pressure of 10 to 15 mmHg to obtain a polyester (b2) having a terminal hydroxyl group.

  To a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 300 parts of ethyl acetate was added, and a solution of 100 parts of DMAc in which 115 parts of 2-furancarboxylic acid chloride was dissolved was slowly added under water cooling, and reacted at room temperature for 4 hours. After the reaction, ethyl acetate, DMAc and excess furancarboxylic acid chloride were removed under reduced pressure to obtain polyester (C-2) having a furan group at the terminal.

(Prepolymer Production Example-3)
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 339.2 parts of bis (4- (2-hydroxyethoxy) phenyl) hexafluoroisopropylidene, 4,4 ′-(3-hydroxypropyloxy) biphenyl 138 parts and 166 parts of terephthalic acid were polycondensed at 200 ° C. for 10 hours under normal pressure. Next, the reaction product was reacted for 5 hours while dehydrating at a reduced pressure of 10 to 15 mmHg to obtain a polyester (b2) having a terminal hydroxyl group.

  Further, 300 parts of ethyl acetate was added thereto, and a solution of 100 parts of DMAc in which 80 parts of water-cooled acrylic acid chloride was dissolved was slowly added and reacted at room temperature for 4 hours. After the reaction, polyester (C-3) having an acryloyl group at the terminal was obtained by removing ethyl acetate, DMAc and excess allylic acid chloride under reduced pressure.

(Toner Production Example-1)
In a beaker, 80 parts of the prepolymer (C-1) obtained in Prepolymer Production Example-1, 80 parts of the prepolymer (C-3) obtained in Prepolymer Production Example-3, and polyester (a) 40 80 parts of WEP-5 (Japanese fats and oils) as a release agent and 200 parts of ethyl acetate were added and dissolved by stirring. Separately, 5 parts of copper phthalocyanine blue pigment and 100 parts of ethyl acetate in a bead mill were mixed with the pigment dispersion which had been dispersed for 30 minutes, and the above-mentioned dissolved material was mixed at 40 ° C. with a TK homomixer at 12000 rpm for 7 minutes. Stir. The obtained dispersion was designated as toner material oil dispersion (1-1).

  Put 400 parts of ion-exchange water, 200 parts of tricalcium phosphate 10% suspension, 0.2 parts of dodecyl sulfate Na salt (SDS) into a 2L mayonnaise bottle, and Cleamix-1.5S (M Technique Co., Ltd.) The toner material oil-based dispersion (1-1) was added to this aqueous dispersion while stirring at 10,000 rpm, and the temperature was raised to 40 ° C. for 20 minutes and then to 70 ° C., and stirring was continued for 60 minutes.

  The organic solvent was removed from the dispersion after the reaction at 50 ° C. under reduced pressure for 1.0 hour, followed by filtration and reslurry washing with 1 L of ion exchange water. Washing and filtration were repeated 4 times. The slurry was blown and dried in an oven at 40 ° C. to obtain spherical toner particles (volume average particle diameter 5.0 μm). The toner particles had an average circularity of 0.980 and a softening point of 103 ° C.

  Next, with respect to the toner particles, 0.4% by weight of hydrophobic silica (manufactured by Hoechst Japan Co., Ltd .: H2000) and 0.6% by weight of hydrophobic titania (manufactured by Titanium Industry Co., Ltd .: STT30A) are used as external additives. Cyan toner C was obtained by adding them in proportion and mixing them with a Henschel mixer.

(Moisture absorption evaluation)
3 g of the obtained toner was placed in a 50 ml polybin, and the humidity was adjusted (exposure left) for 24 hours in an open state in which each sample bottle was opened in each environmental chamber at 30 ° C.-85% RH and 10 ° C.-15% RH.

  Using a HR73 halogen moisture meter (Mettler Toledo), the sample after humidity adjustment was heated at 105 ° C., and the moisture content was measured. The moisture content of each humidity control sample is summarized in Table 1.

Example 2 to Example 5
In Example 2, the type of prepolymer was a combination of polyester C-2 (Prepolymer Production Example-2) and polyester C-3 (Prepolymer Production Example-3), and in Examples 3 to 5, the pigment was changed. Except for the above, a toner was prepared and evaluated in the same manner as in Example 1. The combinations and evaluation results are summarized in Table 1.

Comparative Example 1
The terminal isocyanate prepolymer prepared as described below was used, and in the toner preparation, dilution with ethyl acetate was not performed, but 80 parts of wax WEP-5 was directly added to 440 parts of the prepolymer solution (D-1) prepared below. A toner was prepared and evaluated in the same manner as in Example 1 except that 40 parts of ion exchange water in which 10 parts of 1,6-hexamethylenediamine was dissolved was added to the aqueous phase during dispersion and reaction. The results are summarized in Table 1.

  In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 340 parts of bis (4- (2-hydroxyethoxy) phenyl) isopropylidene, 24 parts of hexamethylene diamine catalyzing isocyanate, 100 of isophthalic acid Part, 66 parts of terephthalic acid and 20 parts of dibutyltin dioctanoic acid were added and reacted at 200 ° C. for 8 hours at normal pressure. Furthermore, after reacting for 5 hours while dehydrating at a reduced pressure of 10 to 15 mmHg, the mixture was cooled to 80 ° C. Subsequently, it reacted with 188 parts of xylylene diisocyanate in a mixed solvent of 500 parts of ethyl acetate dehydrated with molecular sieves and 50 parts of auxiliary solvent DMAc to obtain an isocyanate group-containing prepolymer (D-1).

Evaluation of actual machine The cyan, magenta, yellow and black toners obtained in Example 1, Example 3, Example 4 and Example 5 were electrophotographic society chart 1995 No5- in color laser printer magicolor 2300 DL (manufactured by Minolta). When 1 was output, the image quality was completely satisfactory.
When a toner whose moisture content exceeds 30% at 30 ° C./85% RH in the above-described moisture absorption evaluation is used in an actual machine in a 30 ° C./85% RH environment, the charge amount decreases, image fogging occurs, or charging failure occurs. There is a problem that toner is scattered from the developing machine.

Claims (5)

Dissolving the first polyester prepolymer having a conjugated double bond capable of Diels-Alder reaction, the second polyester prepolymer having multiple bonds capable of Diels-Alder reaction, and the polyester prepolymer containing the first and second reactive groups Toner material oil dispersion containing at least a possible organic solvent is dispersed in an aqueous medium to prepare an oil-in-water (O / W) dispersion, and the chain is extended and cross-linked by Diels-Alder reaction A method for producing toner particles, comprising a step of forming a binder resin .   The first polyester prepolymer and the second polyester prepolymer are derived from a polyester prepolymer obtained by polycondensation of bis (4- (2-hydroxyethoxy) phenyl) hexafluoroisopropylidene and terephthalic acid, The method for producing toner particles according to claim 1.   The method for producing toner particles according to claim 1, wherein the conjugated double bond capable of Diels-Alder reaction is derived from a furyl group.   4. The method for producing toner particles according to claim 1, wherein the multiple bond capable of Diels-Alder reaction is derived from an acryloyl group. (A) a step of polycondensing a polyol component and a polycarboxylic acid component to form a polyester prepolymer,
(B) Using the polyester prepolymer obtained in the above step (A), the first reactive group-containing polyester prepolymer having a conjugated double bond capable of Diels-Alder reaction derived from a furyl group, and derived from an acryloyl group Forming a second reactive group-containing polyester prepolymer having multiple bonds capable of Diels-Alder reaction;
(C) An oily dispersion obtained by dissolving or dispersing a first reactive group-containing polyester prepolymer, a second reactive group-containing polyester prepolymer, and a desired toner additive in an organic solvent is dispersed in an aqueous medium. Preparing an oil-in-water (O / W) dispersion by forming a polyester binder resin subjected to chain extension and crosslinking by Diels-Alder reaction, and
(D) removing the organic solvent from the system to form resin particles, and drying the resin particles to obtain toner particles;
A method for producing toner particles, comprising: